CN1189498A - Method for preparing carbamido tetra-al-alphospho acid and sodium salt and its application - Google Patents
Method for preparing carbamido tetra-al-alphospho acid and sodium salt and its application Download PDFInfo
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- CN1189498A CN1189498A CN 97108420 CN97108420A CN1189498A CN 1189498 A CN1189498 A CN 1189498A CN 97108420 CN97108420 CN 97108420 CN 97108420 A CN97108420 A CN 97108420A CN 1189498 A CN1189498 A CN 1189498A
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Abstract
A new compound (tetramethylene urcidophosphonic acid) and its sodium salt, their preparing process, and its application as scale-resistant corrosion inhibitor in water treatment are disclosed. Its advantages include high scale-resistant corrosion-inhibiting effect, wide application range, easy preparing. It can be used in water system where scale is easily generated and apparatus is easily corroded.
Description
The invention belongs to new compound of ureido derivatives and preparation method thereof, relate to its application as anti-incrustation corrosion inhibitor in the water treatment.
By retrieval, do not find the record and the application of relevant urea groups tetramethyl fork phosphonic acids and sodium salt thereof.
The anti-incrustation corrosion inhibitor that the organic phospho acid compound is used as water treatment has experienced the development of decades at the water treatment field dominate.The first-generation is with Amino Trimethylene Phosphonic Acid (AMP) and 1-hydroxy ethylidene-1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) has been ruled recent two decades for representative, and the not anti-chlorine of AMP is corrosive to non-ferrous metal; The chlorine-resistant property of HEDP is more quite a lot of than AMP, but can generate the calcium salt of microsolubility under the calcium ion of high density, has limited its range of application.2-phosphonic acids butane-1,2 has appearred to the seventies, 4-tricarboxylic acid (PBTCA), and it is widely used in the processing of recirculated cooling water, and it is very stable to the oxidisability biocide, and is big to the tolerance of calcium ion, is applicable to the water treatment of high rigidity; But its corrosion inhibition is limited, and need be used with metal ion just has corrosion mitigating effect; Its synthetic method is complicated in addition, and desired raw material is phosphorous acid two formicesters, dimethyl maleate, vinylformic acid formicester and catalyzer, and is all more expensive.Novel corrosion inhibitor 2-hydroxyl-phosphino-acetate that external the eighties is released is the most effective now organic phospho acid inhibiter; It uses separately, and the concentration in water is 3mg/L, and corrosion inhibition rate is 53.3%; Compositely add in the entry by 6mg/L concentration by 1: 1 with zinc, corrosion inhibition rate can reach 98.1% (" Treatment of Industrial Water ", 1996,16 (3)); US3,032,500 (1962), US4,370,280 (1983) and US4,689,200 (1987) have all put down in writing the synthetic method of 2-hydroxyl-phosphino-acetate, and its method is fairly simple, but raw materials used very expensive.Enter the nineties people be devoted to the 4th generation product research and development, representative is polyamines Quito ether methylenephosphonic acid and phosphono-carboxylic acids; The former has very strong scale inhibition ability to lime carbonate, calcium sulfate and Calucium Silicate powder, and can stablize the oxide compound of iron, zinc, manganese well, and dispersive ability is strong, is specially adapted to the high concentration multiple operation, and its synthetic main raw material is the diamine compound that contains the polyether base; And the latter has good lime carbonate and calcium phosphate scale inhibition ability in cooling water system, good particles dispersed and certain corrosion inhibition are arranged again, work hardly with chlorine, it is a kind of multi-functional medicament, its molecular weight is more than 2000, the synthetic main raw material is the polymkeric substance that contains carboxyl, so think that it is the combination of organic phospho acid and polymkeric substance; Obviously the synthesis material complex structure of the two is very expensive before and after, and the synthesis technique complexity.
The objective of the invention is to propose a kind of new compound, promptly the urea groups tetramethyl is pitched phosphonic acids and sodium salt thereof, and enough simple methods of energy and cheap raw material synthesize, and enables to use as anti-incrustation corrosion inhibitor in the water treatment.
The present invention synthesizes new compound, urea groups tetramethyl fork phosphonic acids and sodium salt thereof.Its molecular structural formula is:
When R is H in the formula, be called urea groups tetramethyl fork phosphonic acids, molecular formula is (H
2O
3PCH
2)
2NCON (CH
2PO
3H
2)
2, molecular weight is 436.08, is the yellow heavy-gravity transparent liquid of tea, and is water-soluble.
When R is Na in the formula, be called urea groups tetramethyl fork Alendronate, molecular formula is (Na
2O
3PCH
2)
2NCON (CH
2PO
3Na
2)
2, molecular weight is 612.00, is white crystal, and is water-soluble.
Urea groups tetramethyl fork phosphonic acids has two kinds of synthetic methods, a kind of is to be raw material with urea, phosphorous acid and formaldehyde, 1: 4 by weight～6: 5～9 ratio, earlier urea and phosphorous acid are inserted constantly stirring in the diluted hydrochloric acid medium, and be heated to reflux state, add formaldehyde again, still keep reflux state to react afterwards 2-4 hour, reaction finishes, and the evaporation concentration reactant obtains urea groups tetramethyl fork phosphonic acids liquid product.Wherein the concentration of dilute hydrochloric acid is 8-18%, and its amount should be greater than the amount sum of urea and phosphorous acid and less than the total amount of urea, phosphorous acid and formaldehyde.
Another kind is to be raw material with urea, phosphorus trichloride, formaldehyde and water, and its usage ratio is respectively in mol: 1-1.4: 4～5.5: 4.4～7.2: 16-40; Add urea and phosphorus trichloride earlier under constantly stirring, and be heated to reflux state in water, add formaldehyde again, still keep reflux state afterwards, reacted 2-4 hour, reaction finishes, and the evaporation concentration reactant obtains urea groups tetramethyl fork phosphonic acids liquid product.
Urea groups tetramethyl fork sodium phosphate synthetic is to be 1 with mol ratio: the urea groups tetramethyl phosphonic acids of 8-10 and sodium hydroxide are raw material, under whipped state, in urea groups tetramethyl fork phosphonic acids, add aqueous sodium hydroxide solution, the two reaction produces precipitation, precipitation, drip washing are separated out in filtration. and drying obtains content and pitches the Alendronate crystal greater than 95% urea groups tetramethyl.
Urea groups tetramethyl fork phosphonic acids and sodium salt thereof are as the application of anti-incrustation corrosion inhibitor in water treatment, can use separately, also can with the composite use of other materials, be applicable to and handle the water that easily generates incrustation scale and produce the corrosive water system that the usage quantity of arbitrary medicament that it is independent or composite is 1.5-25ppm.Its temperature range that is suitable for is 30-100 ℃, and the pH value scope that is suitable for is 5-11, and is applicable to the water of general and high rigidity.Its usage quantity is that the specific requirement of temperature, PH, hardness and water treatment according to treating water is adjusted, and generally is that the high more usage quantity of hardness is big more.Its result of use records scale inhibition performance greater than 95% with the static-state scale inhibition method, and recording corrosion inhibition rate with static steel method and rotary hanging plate method (Chinese chemical industry standard HG/T 2159-91) is 30-98%, and the cycles of concentration of recirculated cooling water can reach 5-10 doubly.
Wherein the amount ranges used separately of urea groups tetramethyl fork phosphonic acids is 1.5-6ppm, uses after being made into the aqueous solution, and its scale inhibition performance is greater than 95%, and corrosion inhibition rate is greater than 30%.The amount ranges that urea groups tetramethyl fork Alendronate uses is separately used after being made into the aqueous solution between 2-9ppm, and scale inhibition performance is greater than 95%, and corrosion inhibition rate is greater than 50%.
The prescription of composite anti-incrustation corrosion inhibitor is (by weight), urea groups tetramethyl fork phosphonic acids 10-40; Phosphonate group dibasic amino acid 1-5; The amino di-alcohol 1-5 of phosphonate group; Inorganic salt 1-4, wherein inorganic salt can be borax, zinc sulfate, Sodium orthomolybdate etc.Because the molecular weight ratio urea groups tetramethyl of urea groups tetramethyl fork Alendronate fork phosphonic acids is many 40%, so when replacing the urea groups tetramethyl pitch phosphonic acids in compounded formula with urea groups tetramethyl fork Alendronate, the corresponding increase by 40% of its weight ratio is 14-56.Press the composite anti-incrustation corrosion inhibitor of above-mentioned prescription in use, according to handling its amount ranges of water hardness between 2-25ppm.Its scale inhibition performance is greater than 98%, and corrosion inhibition rate is greater than 95%.
The present invention compared with prior art has following advantage aspect water treatment: adopt the composite anti-incrustation corrosion inhibitor of the present invention to compare with 2-hydroxyl-phosphino-acetate, and the corrosion inhibition basically identical, but the former scale-inhibiting properties is better, and synthetic cost only is the latter's 30-40%; Compare with PBTCA, polyamines Quito ether methylenephosphonic acid, phosphono-carboxylic acids, its anticorrosion-antiscaling property and other performances are all similar, but preparation method of the present invention is simple, raw material cheap, cost is very low.
Below describe specific embodiments of the present invention in detail.
Embodiment 1. is that 1: 5.9 urea and phosphorous acid are inserted in 12% the dilute hydrochloric acid with the ingredients by weight ratio, the amount of dilute hydrochloric acid is 13, constantly stir, reaction mass is heated to reflux state, the adding weight ratio is 9 formaldehyde, still keep reflux state to react 3.5 hours after adding, reaction finishes, and evaporation concentration reactant 1 hour obtains urea groups tetramethyl fork phosphonic acids content greater than 25% liquid product, its transformation efficiency is 82.9%, and the effective phosphine of colorimetric method for determining is adopted in its quantitative assay.
Embodiment 2. constantly stirs in the water of 30.4mol, add the urea of 1.08mol and the phosphorus trichloride of 4.2mol respectively, and be heated to reflux state, the formaldehyde that adds 6.24mol, still keep reflux state to react 2 hours after adding, reaction finishes, evaporation concentration reactant 1 hour, obtain urea groups tetramethyl fork phosphonic acids content and be 25.9% liquid product, its transformation efficiency is 92.4%.
Embodiment 3. restrains the aqueous solution that contains sodium hydroxide 40% toward adding 103 during 100 grams contain the aqueous solution of urea groups tetramethyl fork phosphonic acids 50% under room temperature constantly stirs, its mol ratio is 1: 9, the two reaction produces precipitation, precipitation is separated out in filtration, drip washing, drying, obtain content and be 97.1% urea groups tetramethyl fork Alendronate crystal, transformation efficiency is 98.4%.
Embodiment 4. contains calcium ion 37.59mg, magnesium ion 21.59mg, chlorion 29.68mg, carbonate 5.15mg, bicarbonate radical 453.67mg at one liter, PH is in 7.85 the water sample, adding content and be 30% urea groups tetramethyl fork phosphonic acids aqueous solution 7mg (for 2.1ppm) stirs evenly, the A3 steel disc is suspended in the sample water, and with sample water 45 ± 1 ℃ of constant temperature 120 hours, it is 100% that the taking-up steel disc records scale inhibition performance by the static-state scale inhibition method, and recording corrosion inhibition rate by the static steel method is 32.15%.
Embodiment 5. adds content in one liter of sample water identical with example 4 be that 30% urea groups tetramethyl fork Alendronate aqueous solution 10mg (for 3ppm) stirs evenly, the A3 steel disc is suspended in the sample water, and with sample water 45 ± 1 ℃ of constant temperature 120 hours, it is 100% that the taking-up steel disc records scale inhibition performance by the static-state scale inhibition method, and recording corrosion inhibition rate by the static steel method is 53.80%.
Embodiment 6. contains calcium ion 62.14mg, magnesium ion 21.63mg, chlorion 45.46mg, bicarbonate radical 258.9mg, water-insoluble 0.047% at one liter, PH is in 7.89 the sample water, adding composite weight ratio is 36: 1: 5: the composite anti-incrustation corrosion inhibitor 6.5mg of 3 urea groups tetramethyl fork phosphonic acids, phosphonate group dibasic amino acid, the amino di-alcohol of phosphonate group and zinc sulfate adds with aqueous solution form.The A3 steel disc is placed on earlier to contain Sodium hexametaphosphate 99 600ppm, Zinc Sulphate Heptahydrate 200ppm, PH be that pre-film was handled 48 hours in 6.0～6.5 the pre-film liquid, take out again and hung in the sample water 45 ± 1 ℃ of constant temperature 120 hours, it is 100% that the taking-up steel disc records scale inhibition performance by the static-state scale inhibition method, and recording corrosion inhibition rate by the static steel method is 95.67%.
Embodiment 7. adds composite weight ratio in one liter of sample water identical with example 6 be 36: 1: 5: the composite anti-incrustation corrosion inhibitor 6.5mg of 3 (for borax) adds with aqueous solution form.A3 steel disc and example 6 are carried out pre-film equally handle, hung in the sample water 45 ± 1 ℃ of constant temperature again 120 hours, taking out and recording scale inhibition performance is 100%, and corrosion inhibition rate is 97.3%.
Embodiment 8. adds composite weight ratio in one liter of sample water identical with example 6 be 36: 1: 5: the composite anti-incrustation corrosion inhibitor 6.5mg of 3 (for Sodium orthomolybdate) adds with aqueous solution form.A3 steel disc and example 6 are carried out pre-film equally handle, hung in the sample water 45 ± 1 ℃ of constant temperature again 120 hours, taking out and recording scale inhibition performance is 100%, and corrosion inhibition rate is 98.7%.
Embodiment 9. adds composite weight ratio in one liter of sample water identical with example 6 be 36: 1: 5: 1.5 (for zinc sulfate): the composite anti-incrustation corrosion inhibitor 6.5mg of 1.5 (for borax) adds with aqueous solution form.A3 steel disc and example 6 are carried out pre-film equally handle, hung in the sample water 45 ± 1 ℃ of constant temperature again 120 hours, taking out and recording scale inhibition performance is 100%, and corrosion inhibition rate is 97.63%.
Embodiment 10. adds composite weight ratio in one liter of sample water identical with example 4 be 20: 5: 1: the composite anti-incrustation corrosion inhibitor 3.4mg of 4 (for zinc sulfate) adds with aqueous solution form.A3 steel disc and example 6 are carried out pre-film equally handle, hung in the sample water 45 ± 1 ℃ of constant temperature again 120 hours, taking out and measuring scale inhibition performance is 100%, and corrosion inhibition rate is 96.56%.
Embodiment 11. adds composite weight ratio in one liter of sample water identical with example 6 be 50 (for urea groups tetramethyl fork Alendronate): the composite anti-incrustation corrosion inhibitor 8.5mg of 1: 5: 3 (being zinc sulfate) adds with aqueous solution form.A3 steel disc and example 6 are carried out pre-film processing equally, hang on 2 centimeters of sample water underwaters again, and pressed 150 rev/mins of rotation steel discs 72 hours, it is 100% that the taking-up steel disc records scale inhibition performance, and recording corrosion inhibition rate by the rotary hanging plate method is 98.61%.
Recirculated cooling water (underground water) the calcium ions 103.49ppm of embodiment 12. 1 smelteries, magnesium ion 60.5ppm, bicarbonate radical 209.38ppm, chlorion 102.51ppm, PH are 8.22, and its range of temperature is 30-85 ℃.According to this hardness, with composite weight ratio is 35: 4: 4: the composite anti-incrustation corrosion inhibitor of 2 (for zinc sulfate) adds by water 10 grams per ton, add in the recycle pump treatment system with aqueous solution form, when needing make up water, the dose of adding that calculates is joined in the make up water in system.After 12 months, cut one section circulating pipe, actual observation and use apparatus measures, result are the smooth nothing dirts of water pipe internal surface, and the thickness of tube wall does not change.Long-standing fouling and rotten dirty problem have been solved.
Former water calcium ions 62.14ppm, magnesium ion 21.63ppm, chlorion 45.46ppm, bicarbonate radical 258.9ppm, water-insoluble 0.04% that embodiment 13. 1 hot water circulation boilers are used, PH is 7.89, range of temperature 65-95 ℃.According to this hardness, with composite weight ratio is 50 (for urea groups tetramethyl fork Alendronate): the composite anti-incrustation corrosion inhibitor of 1: 5: 3 (for zinc sulfate) adds by water 8.5 grams per ton, in boiler, add water by the recycle pump place with aqueous solution form, when boiler needs make up water, the dose of adding that calculates is joined in the make up water.Turn round after 40 months, this hot water circulation boiler moves normally always.Regularly open boiler every year, actual observation and use apparatus measures, result are the smooth nothing dirts of water pipe internal surface, and thickness of pipe does not change, and has solved long-standing fouling and etching problem.
Claims (9)
1. a ureido derivatives is characterized in that, its molecular structural formula is:
When R is H in the formula, be called urea groups tetramethyl fork phosphonic acids, molecular formula is (H
2O
3PCH
2)
2NCON (CH
2PO
3H
2)
2, molecular weight is 436.08, is the yellow heavy-gravity transparent liquid of tea, and is water-soluble; When R is Na in the formula, be called urea groups tetramethyl fork Alendronate, molecular formula is (Na
2O
3PCH
2)
2NCON (CH
2PO
3Na
2)
2, molecular weight is 612.00, is white crystal, and is water-soluble.
2. one kind prepares the described urea groups tetramethyl fork of claim 1 phosphonic method, it is characterized in that, be to be raw material with urea, phosphorous acid and formaldehyde, 1: 4 by weight～6: 5～9 ratio is inserted urea and phosphorous acid in the diluted hydrochloric acid medium earlier and is constantly stirred, and be heated to reflux state, add formaldehyde again, still keep reflux state to react afterwards 2-4 hour, reaction finishes, the evaporation concentration reactant obtains urea groups tetramethyl fork phosphonic acids liquid product.
3. preparation method according to claim 2 is characterized in that, the concentration of described dilute hydrochloric acid is 8-18%, and its consumption is greater than the amount sum of urea and phosphorous acid, and less than the total amount of urea, phosphorous acid and formaldehyde.
4. one kind prepares the described urea groups tetramethyl of claim 1 fork phosphonic method, it is characterized in that, is to be raw material with urea, phosphorus trichloride, formaldehyde and water, and its usage ratio is respectively in mol: 1～1.4: 4～5.5: 4.4～7.2: 16～40; Under constantly stirring, in water, add urea and phosphorus trichloride earlier, and be heated to reflux state, add formaldehyde again, still keep reflux state reaction 2-4 hour afterwards, reaction finishes, and the evaporation concentration reactant obtains urea groups tetramethyl fork phosphonic acids liquid product.
5. one kind prepares the method that the described urea groups tetramethyl of claim 1 is pitched Alendronate, it is characterized in that, be to be that 1: 8～10 urea groups tetramethyl fork phosphonic acids and sodium hydroxide are raw material with mol ratio, under whipped state, in urea groups tetramethyl fork phosphonic acids, add aqueous sodium hydroxide solution, the two reaction produces precipitation, precipitation, drip washing, drying are separated out in filtration, obtain urea groups tetramethyl fork Alendronate crystal.
6. the using method of described urea groups tetramethyl fork phosphonic acids of a claim 1 and sodium salt thereof, it is characterized in that, described urea groups tetramethyl fork phosphonic acids and sodium salt thereof can be used for water treatment as anti-incrustation corrosion inhibitor separately or with other material is composite, and its amount ranges is 1.5～25ppm.
7. using method according to claim 6 is characterized in that, the independent amount ranges of urea groups tetramethyl fork phosphonic is 1.5～6ppm; The independent amount ranges of urea groups tetramethyl fork Alendronate is 2～9ppm; The two all is to use after being made into the aqueous solution.
8. using method according to claim 6 is characterized in that, the composite prescription of urea groups tetramethyl fork phosphonic acids and other materials is (weight ratio), urea groups tetramethyl fork phosphonic acids 10～40; Phosphonate group dibasic amino acid 1～5; The amino di-alcohol 1～5 of phosphonate group; Inorganic salt 1～4; Wherein urea groups tetramethyl fork phosphonic acids can be replaced by urea groups tetramethyl fork Alendronate, and the weight ratio after the replacement is 14-56.
9. using method according to claim 8 is characterized in that, described inorganic salt are borax, zinc sulfate, Sodium orthomolybdate.
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|---|---|---|---|
| CN97108420A CN1046124C (en) | 1997-01-26 | 1997-01-26 | Method for preparing carbamido tetra-al-alphospho acid and sodium salt and its application |
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|---|---|---|---|
| CN97108420A CN1046124C (en) | 1997-01-26 | 1997-01-26 | Method for preparing carbamido tetra-al-alphospho acid and sodium salt and its application |
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| CN1046124C CN1046124C (en) | 1999-11-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
| CN109776629A (en) * | 2019-03-07 | 2019-05-21 | 陕西沃利尔精细化工科技有限公司 | Phosphonic acid base urea base glucosan derivative and the preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920733A (en) * | 1973-08-06 | 1975-11-18 | Monsanto Co | Ureidoalkylphosphonic acids |
-
1997
- 1997-01-26 CN CN97108420A patent/CN1046124C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060392A (en) * | 2010-11-22 | 2011-05-18 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN102060392B (en) * | 2010-11-22 | 2012-02-08 | 天津市职业大学 | Method for synthesizing antiincrustation corrosion inhibitor by using waste liquid generated in allantoin production |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
| CN109776629A (en) * | 2019-03-07 | 2019-05-21 | 陕西沃利尔精细化工科技有限公司 | Phosphonic acid base urea base glucosan derivative and the preparation method and application thereof |
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