CN104497042A - Synthesis method and application of low-phosphorous corrosion and scale inhibitor - Google Patents
Synthesis method and application of low-phosphorous corrosion and scale inhibitor Download PDFInfo
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- CN104497042A CN104497042A CN201410770862.2A CN201410770862A CN104497042A CN 104497042 A CN104497042 A CN 104497042A CN 201410770862 A CN201410770862 A CN 201410770862A CN 104497042 A CN104497042 A CN 104497042A
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Abstract
The invention discloses a synthesis method and application of a low-phosphorous corrosion and scale inhibitor. The synthesis method comprises the following steps: adding a certain amount of phosphorous acid and acetylchloride, starting a reflux condensation device and a stirring device and reacting at 40 DEG C for 1.5h; then, slowly increasing the temperature to 115 DEG C and reacting for 1.5h; then, adding a certain amount of n-butyl alcohol, distilling till n-butyl alcohol is completely distilled out to take hydrochloric acid and excessive acetylchloride away; finally, cooling to 60 DEG C, adding a certain amount of water, carrying out hydrolysis reaction for 1, standing and cooling to obtain faint yellow viscous liquid which is the synthesized low-phosphorous corrosion and scale inhibitor. The synthesized low-phosphorous corrosion and scale inhibitor product is low in phosphorous content; after the low-phosphorous corrosion and scale inhibitor is added to circulating water and used, the content of PO4<3-> in the water is low and further less PO4<3-> is discharged; when the addition amount of the low-phosphorous corrosion and scale inhibitor is 5g/m<3>, the scale inhibition rate for the circulating water is 96.70%; and when the addition amount of the low-phosphorous corrosion and scale inhibitor is 70g/m<3>, the corrosion inhibition rate for the circulating water is 88.97%.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of synthetic method and application of low-phosphorus corrosion and scale inhibitor.
Background technology
Along with the environmental consciousness of people strengthens, low-phosphorous and be more and more subject to people's attention without Phosphorus environment-friendly type inhibition anti-sludging agent, the corrosion inhibiting and descaling agents such as molybdate, silicate and tungstate because it is without phosphorus, the characteristic of low toxicity and be applied to industrial circulating cooling water system, but molybdate is expensive, use cost is higher, and tungstate and the silicate anticorrosion-antiscaling effect when single use is undesirable.1-Hydroxy Ethylidene-1,1-Diphosphonic Acid also known as (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid, hydroxy ethylene diphosphonic acid, PO4 in its product
3-content is about 0.5-1.0%.When it makes Scale inhibitors, working concentration is generally 1-10mg/L, and when making inhibiter, working concentration is generally 20-70mg/L, by 70mg/L put into use in recirculated water time water body in PO4
3-content <0.7mg/L, far below general phosphine system medicament PO4 in recirculated cooling water
3-content 3-5mg/L is a kind of corrosion inhibiting and descaling agent of low-phosphorous, low toxicity; It can belong to ion with underwater gold simultaneously, and especially calcium ion forms six-membered ring chelate, under 250 DEG C of conditions, still can play good corrosion-mitigation scale-inhibition effect." water treatment agent and material application manual (second edition) " the 97-98 page report published in June, 2006 is published according to press of CNPC, the synthesis route of current 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid has multiple, and the technique being wherein Material synthesis 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid with phosphorus trichloride, Glacial acetic acid, water is used the most extensive at home and abroad.This synthesis technique mainly utilizes phosphorus trichloride, Glacial acetic acid and water to react and generates phosphorous acid and Acetyl Chloride 98Min., then generates 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid via reactions such as acetyl chemical combination and hydrolysis.But correlated response is not as sequence is carried out in actual synthesis process, but carry out with other side reactions emulative interlocking, reaction process is comparatively complicated, and thus reaction process is difficult to control.A large amount of by products such as hydrogenchloride can be attended by simultaneous reactions process generate, intermediate acetyl chlorine causes Acetyl Chloride 98Min. to lose in a large number due to low easily being taken away by the hydrogen chloride gas produced of boiling point, which not only adds the quantity discharged of " three wastes ", and directly can reduce the yield of product, reduce the economic benefit of enterprise.In order to overcome Problems existing in above-mentioned building-up process, the present invention directly with phosphorous acid, Acetyl Chloride 98Min. and water for raw material, take propyl carbinol as solvent, " single stage method " synthesis low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, and its corrosion and scale inhibition performance is measured.
Summary of the invention
The object of the invention is in traditional 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid synthesis process; the more difficult control of long reaction time, reaction process, with side reaction more; the technical problems such as material loss is larger; directly with phosphorous acid, Acetyl Chloride 98Min. and water for raw material; propyl carbinol is solvent; through acetyl combination reaction and hydrolysis reaction, " single stage method " synthesis of hydroxy ethylene-diphosphonic acid.
Cardinal principle of the present invention utilizes phosphorous acid and Acetyl Chloride 98Min. generation acetyl combination reaction, and then add water to generation product and to be hydrolyzed to it.The reaction formula of " single stage method " is as follows, and wherein reaction formula (1) is phosphorous acid and Acetyl Chloride 98Min. generation acetyl chemical combination reaction process, and reaction formula (2) is the hydrolytic process of reaction formula (1) generation product.
The technical solution used in the present invention is: add in reactor by a certain amount of phosphorous acid and Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add a certain amount of propyl carbinol distillation 1.0h, distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add a certain amount of water and to be hydrolyzed reaction.Place cooling, obtain light yellow viscous liquid, be low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention.It is 1:1.5:1.35:1 that its phosphorous acid, Acetyl Chloride 98Min., propyl carbinol and water add mol ratio.
The synthetic method of this 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention, avoid operational path in prior synthesizing method comparatively complicated, side reaction adjoint in reaction process is more, the more difficult control of reaction process, the shortcomings such as material loss is larger, effectively reduce the discharge of " three wastes "; PO4 in synthesis of hydroxy ethylene-diphosphonic acid of the present invention simultaneously
3-content is only 0.05mg/L, is that 100mg/L is added in recirculated water, PO4 in water body detected by dosage
3-content be only 0.0005mg/L, be medicament PO4 in recirculated cooling water far below general phosphine (phosphorus)
3-content 3-5mg/L.Compared with general phosphine system medicament, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention is added to water body PO4 when using in recirculated water
3-content lower, thus make the PO4 of outer row
3-less, effectively reduce cost for wastewater treatment, decrease pollution on the environment simultaneously.
The present invention carries out corrosion and scale inhibition performance measuring method to sintetics-1-Hydroxy Ethylidene-1,1-Diphosphonic Acid: the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid that the present invention synthesizes is mixed with the aqueous solution by certain mass concentration, adopts " mensuration-tosca method of water conditioner scale-inhibiting properties " (GB/T16632-2008) and " mensuration-rotary hanging plate method of water conditioner corrosion inhibition " (GB/T18175-2000) to carry out scale inhibition respectively, corrosion inhibition measures.
Embodiment
The synthetic method of low-phosphorus corrosion and scale inhibitor provided by the invention is as follows:
Adding in reactor by a certain amount of phosphorous acid and Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add a certain amount of propyl carbinol distillation 1.0h, until distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add a certain amount of water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention.It is 1:1.5:1.35:1 that its phosphorous acid, Acetyl Chloride 98Min., propyl carbinol and water add mol ratio.The present invention's phosphorous acid molecular weight used is 82, and Acetyl Chloride 98Min. molecular weight is 78.5, and the molecular weight of propyl carbinol is 74, and the molecular weight of water is 18, and the molecular weight of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is 206.
The 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention being synthesized is 1kg/m by mass concentration
3and 10kg/m
3be mixed with the aqueous solution, carry out scale inhibition respectively, corrosion inhibition measures.
4 embodiments of the present invention are below provided
Embodiment 1
In reactor, adding 20.50kg phosphorous acid and 29.50kg Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add 25kg propyl carbinol distillation 1.0h, until distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add 4.50kg water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be the low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention's synthesis.When circulating water temperature is 40 DEG C, dosage is 5g/m
3time, scale inhibition performance reaches 89.80%; When circulating water temperature is 45 DEG C, dosage is 40g/m
3time, corrosion inhibition rate reaches 60.04%, when quantity of circulating water is 1000m
3/ h, at least can reduce PO4 every year
3-quantity discharged 26t.
Embodiment 2
In reactor, adding 41.05kg phosphorous acid and 58.05kg Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add 50kg propyl carbinol distillation 1.0h, until distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add 9.00kg water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be the low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention's synthesis.When circulating water temperature is 50 DEG C, dosage is 5g/m
3time, scale inhibition performance reaches 96.70%; When circulating water temperature is 45 DEG C, dosage is 50g/m
3time, corrosion inhibition rate reaches 80.71%, when quantity of circulating water is 2000m
3/ h, at least can reduce PO4 every year
3-quantity discharged 50t
Embodiment 3
In reactor, adding 61.55kg phosphorous acid and 87.55kg Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add 75kg propyl carbinol distillation 1.0h, until distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add 13.50kg water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be the low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention's synthesis.When circulating water temperature is 50 DEG C, dosage is 8g/m
3time, scale inhibition performance reaches 96.30%; When circulating water temperature is 45 DEG C, dosage is 60g/m
3time, corrosion inhibition rate reaches 86.97%, when quantity of circulating water is 3000m
3/ h, can reduce PO4 every year
3-quantity discharged 75t.
Embodiment 4
In reactor, adding 82.05kg phosphorous acid and 118.05kg Acetyl Chloride 98Min., open condensation reflux unit, is 200r/min at magnetic stirrer rotating speed, and temperature is react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react after 1.5 hours and add 100kg propyl carbinol distillation 1.0h, until distill out propyl carbinol to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add 18.00kg water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be the low-phosphorus corrosion and scale inhibitor 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of the present invention's synthesis.When circulating water temperature is 50 DEG C, dosage is 10g/m
3time, scale inhibition performance reaches 92.80%; When circulating water temperature is 45 DEG C, dosage is 70g/m
3time, corrosion inhibition rate reaches 88.97%, when quantity of circulating water is 4000m
3/ h, at least can reduce PO4 every year
3-quantity discharged 100t.
Table 1 medicament synthesizing formula of the present invention, added amount of chemical, temperature are to corrosion and scale inhibition performance test result and CER
Claims (2)
1. the synthetic method of a low-phosphorus corrosion and scale inhibitor and application.It is characterized in that adopting following steps to carry out:
A certain amount of phosphorous acid and Acetyl Chloride 98Min. are added in reactor, opens condensation reflux unit and whipping appts, react 1.5 hours under 40 DEG C of conditions.Then be slowly warmed up to 115 DEG C, react and add a certain amount of propyl carbinol after 1.5 hours and distill, until distill out propyl carbinol completely to take away hydrochloric acid and excessive Acetyl Chloride 98Min..Finally cool to 60 DEG C, add a certain amount of water and to be hydrolyzed reaction 1 hour.Place cooling, obtain light yellow viscous liquid, be the low-phosphorus corrosion and scale inhibitor of the present invention's synthesis.
2. the synthetic method of a kind of low-phosphorus corrosion and scale inhibitor according to claim 1 and application.It is characterized in that: the molecular weight of phosphorous acid is 82, and Acetyl Chloride 98Min. molecular weight is 78.5, the molecular weight of propyl carbinol is 74, and the molecular weight of water is 18.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB978297A (en) * | 1961-07-03 | 1964-12-23 | Henkel & Cie Gmbh | Process for the preparation of derivatives of phosphorous acid |
| CN103073579A (en) * | 2013-01-09 | 2013-05-01 | 江苏大明科技有限公司 | Production technology for HEDP with low arsenic content |
| CN103145757A (en) * | 2013-02-25 | 2013-06-12 | 枣庄市鑫泰水处理技术有限公司 | Production process of HEDP.Na4 (tetrasodium of 1-hydroxy ethylidene-1,1-diphosphonic acid) solid |
| CN104478924A (en) * | 2014-12-15 | 2015-04-01 | 常州大学 | 'One-step process' synthetic method of hydroxyethylidene diphosphonic acid |
-
2014
- 2014-12-15 CN CN201410770862.2A patent/CN104497042A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB978297A (en) * | 1961-07-03 | 1964-12-23 | Henkel & Cie Gmbh | Process for the preparation of derivatives of phosphorous acid |
| CN103073579A (en) * | 2013-01-09 | 2013-05-01 | 江苏大明科技有限公司 | Production technology for HEDP with low arsenic content |
| CN103145757A (en) * | 2013-02-25 | 2013-06-12 | 枣庄市鑫泰水处理技术有限公司 | Production process of HEDP.Na4 (tetrasodium of 1-hydroxy ethylidene-1,1-diphosphonic acid) solid |
| CN104478924A (en) * | 2014-12-15 | 2015-04-01 | 常州大学 | 'One-step process' synthetic method of hydroxyethylidene diphosphonic acid |
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Application publication date: 20150408 |