CN101792504B - Methods for preparing and applying modified polyaspartic acid scale inhibitor - Google Patents
Methods for preparing and applying modified polyaspartic acid scale inhibitor Download PDFInfo
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- CN101792504B CN101792504B CN2010101264297A CN201010126429A CN101792504B CN 101792504 B CN101792504 B CN 101792504B CN 2010101264297 A CN2010101264297 A CN 2010101264297A CN 201010126429 A CN201010126429 A CN 201010126429A CN 101792504 B CN101792504 B CN 101792504B
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Abstract
The invention relates to methods for preparing and applying a modified polyaspartic acid scale inhibitor, which belong to the field of preparation and application of scale inhibitors. The method for preparing the modified polyaspartic acid scale inhibitor comprises the following step of: preparing polysuccinimide (PSI), polyaspartic acid (PASP) and modified polyaspartic acid (CSN-PASP). The scale inhibitor prepared by using the method has good adaptability at the temperature of 50-80 DEG C and the pH value ranging from 6.0 to 8.5. The modified polyaspartic acid scale inhibitor belongs to a polymer type scale inhibitor. A PASP molecule does not contain phosphorus, has no poison, does not destroy the ecological environment and has favorable biodegradability and water solubility, and the excellent scale inhibiting dispersion performance is particularly suitable for industrial water treatment. The aim for improving the scale inhibiting performance of the PASP is achieved by just adding a micromolecule substance in synthesis without changing other process conditions.
Description
Technical field:
The present invention relates to the technology of preparing of modified polyaspartic acid scale inhibitor.Relate in particular to a kind of preparation and application method thereof that is used for the water conditioner modified polyaspartic acid scale inhibitor.
Technical background:
In recent years, along with industrial expansion, water consumption increases day by day in the Industrial processes, and RESEARCH ON SCALE INHIBITOR is extraordinarily paid attention to.In numerous Scale inhibitorss, all there is Scale inhibitors use cost height, the low and environmentally harmful problem of scale inhibition efficient, the green scale inhibitor of at home and abroad generally acknowledging and the renewal product of water treatment have at present become the focus of research and development.Studies show that optimizing synthesis condition increases new functional group by polymeric modification on the PASP main chain, it is multi-functional that PASP is had, and is the new trend to the research of PASP Scale inhibitors.
Summary of the invention:
The objective of the invention is to solve existing Scale inhibitors use cost height, low and the environmentally harmful problem of scale inhibition efficient, one provide a kind of in water solvability good, nontoxic to environment, biodegradable, scale inhibition efficient height, the modified polyaspartic acid scale inhibitor synthetic method that production cost is low, two provide a kind of application method of modified polyaspartic acid scale inhibitor, have increased its range of application.
Realize above-mentioned purpose by the following technical solutions: a kind of preparation method of modified polyaspartic acid scale inhibitor, described method comprises the steps:
A. prepare polysuccinimide (PSI)
1. add 29-30g maleic anhydride and 55-65mL deionized water and stirring in the container, being warming up to and dripping massfraction after 80-90 ℃ is 25% ammoniacal liquor 45mL, obtains colourless solution after ammoniacal liquor dropwises, under 75-85 ℃, stir 2h, suspended substance is dissolved fully, must clarify homogeneous phase solution;
2. the homogeneous phase solution that 1. step is made is 90 ℃ of following underpressure distillation, obtain the mixture of white crystal and a small amount of thick liquid, add that to be heated to dissolution of crystals once more behind the 40-45mL deionized water be liquid in the mixture, this liquid is cooled off in ice bath, have crystal to separate out through cooling, suction filtration obtains white plates crystal maleimide;
3. the white plates crystal maleimide that 2. step is made adds the 20-30ml deionized water dissolving, is placed on methyl-silicone oil oil bath generation condensation reaction and obtains brown solid, is polysuccinimide; (PASP)
B. the preparation of poly aspartic acid (PASP) and modified polyaspartic acid (being called for short CSN-PASP)
1. 1/2 of the polysuccinimide quality that 3. top step is made be contained in the there-necked flask, there-necked flask is placed in 50-90 ℃ the water-bath, the deionized water that adds 10mL, NaOH solution titration hydrolysis with 2mol/L, obtain the solution of reddish-brown pH value between 8.5-12, red tan solution less than 100 ℃ of underpressure distillation, is removed moisture, be put into then that drying obtains reddish-brown solid poly aspartic acid in the baking oven;
2. getting 1/2 of polysuccinimide quality that 3. step make packs in the there-necked flask, add N according to the 1g/5mL volume, in the N solvent dimethylformamide (commercially available organic solvent), in solvent, add the 1g thiocarbamide, normal temperature is used magnetic stirrer 1.5 hours down, obtain blood red clear solution, the sodium hydroxide solution that in blood red clear solution, adds 3mol/L, hydrolysis is 1 hour in 50 ℃ water bath with thermostatic control, solution is splashed in the beaker that adds 3-4 times of volume of ethanol at last, and under the situation of magnetic agitation, make it to precipitate, get the thick thing of reddish-brown, remove supernatant liquid, dry under the infrared drying lamp, finally obtain faint yellow end product modified polyaspartic acid scale inhibitor (being called for short CSN-PASP), the airtight preservation of porphyrize is standby.
A kind of application method of modified polyaspartic acid scale inhibitor, described modified polyaspartic acid scale inhibitor (be called for short CSN-PASP) be 50～80 ℃ of temperature, and the pH value is in 6.0～8.5 the scope, to have excellent adaptability.
The synthetic of poly aspartic acid makes through monomer polymerization-hydrolysis-purification.The aspartic acid polymerization generates polysuccinimide (PSI), and latter's hydrolysis in alkaline aqueous solution, open loop generate poly aspartic acid.Generally be at present under the NaOH hydrolysising condition, the PSI hydrolysis generate have-OH and-PASP of NH, if make its open loop can obtain different PASP derivatives and select different media and PSI to react, after adding some group on the main chain of PASP, can improve its linear structure, increase polymkeric substance Ca
2+Huge legendary turtle close ability, thereby improve the scale inhibition ability of polymkeric substance.
The modified polyaspartic acid scale inhibitor of the present invention's preparation belongs to the polymer-type Scale inhibitors.Not phosphorous, nontoxic in poly aspartic acid (PASP) molecule, do not destroy ecotope and have good biodegradability and water-soluble, its excellent scale inhibition and dispersion performance is specially adapted to Treatment of Industrial Water.Its great advantage is the processing condition that need not change other, just adds a kind of small-molecule substance in synthetic, and reached the purpose that increases the scale-inhibiting properties of poly aspartic acid.
Description of drawings:
Fig. 1 is that temperature of the present invention influences synoptic diagram to the CSN-PASP scale-inhibiting properties.
Fig. 2 is the synoptic diagram of pH of the present invention to the influence of CSN-PASP scale-inhibiting properties.
Fig. 3 a, b are lime carbonate crystalline form SEM figure of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
1, the modified polyaspartic acid scale inhibitor preparation method is as follows:
(1) preparation of polysuccinimide (PSI)
1. under condition of stirring, in the 250mL four-hole boiling flask, add 29.4g maleic anhydride and 60mL deionized water, being warming up to and dripping massfraction after 85 ℃ is 25% ammoniacal liquor 45mL.After dropwising, ammoniacal liquor gets a colourless solution.Under 75-85 ℃, stirred 2 hours, suspended substance is dissolved fully, must clarify homogeneous phase solution.
2. with step homogeneous phase solution 1. 90 ℃ of following underpressure distillation, the mixture of white crystal and a small amount of thick liquid.Be heated to dissolution of crystals once more after adding about 45mL deionized water.Liquid is cooled off in ice bath, have crystal to separate out, suction filtration gets white plates crystal maleimide.
3. the white plates crystal maleimide that 2. step is made adds the 20-30ml deionized water dissolving, is placed on methyl-silicone oil oil bath generation condensation reaction and obtains brown solid 24.2g, is polysuccinimide.
2, the preparation of poly aspartic acid (PASP) and modified polyaspartic acid (being called for short CSN-PASP)
1. will fill in the water-bath that 1/2 the there-necked flask that newly makes the polysuccinimide quality is placed on 50-90 ℃, add the water of 10mL, with the NOaH solution titration hydrolysis of 2mol/L, behind about 40min, solid dissolves fully, and solution is reddish-brown, and the pH value gets final product between 8.5-12.Red tan solution less than 100 ℃ of underpressure distillation, is removed moisture, be put into then that drying obtains reddish-brown solid poly aspartic acid (PASP) in the baking oven.
2. getting remaining 1/2 (quality) polysuccinimide packs in the there-necked flask, the 1g/5mL volume adds N, in N dimethyl formamide (DMF) solvent (commercially available solvent), in this solvent, add 1g thiocarbamide (being called for short CSN), normal temperature is used the magnetic stirrer some hrs down, gets blood red clear solution.The sodium hydroxide solution hydrolysis some hrs in 50 ℃ water bath with thermostatic control that adds 3mol/L, solution is splashed in the beaker that adds 3-4 times of volume of ethanol at last, and under the situation of magnetic agitation, make it to precipitate, get the thick thing of reddish-brown, remove supernatant liquid, dry under the infrared drying lamp, the final faint yellow end product modified polyaspartic acid (being called for short CSN-PASP) that gets, the airtight preservation of porphyrize is standby.
Using method embodiment
Embodiment 1:
In 1 premium on currency, be made into CSN and 6mg/L self-control PASP and the 6mg/L CSN compositional liquor of CSN-PASP, 12mg/L self-control PASP, the 12mg/L of 12mg/L respectively at volumetric flask according to the mass concentration proportioning, pour in the Erlenmeyer flask then, tight with the plug lid that has Glass tubing, the scale inhibition performance of mensuration medicament behind the heating 10h in 80 ℃ water bath with thermostatic control.The results are shown in Table 1.
Table 1
Embodiment 2
In 1 premium on currency, be made into the scale inhibition liquid of the CSN-PASP of 12mg/L according to the mass concentration proportioning, place the resistance calcium carbonate scale scale inhibition performance of measuring medicament behind the water bath with thermostatic control heating 10h of 60 ℃, 70 ℃, 80 ℃ and 90 ℃ respectively.Temperature less than 80 ℃ of situations under, Scale inhibitors all has excellent adaptability.The result as shown in Figure 1.
Embodiment 3
In 1 premium on currency, the scale inhibition liquid of the CSN-PASP that contains 12mg/L, be mixed with pH respectively and be respectively 6.0,7.0,8.0,9.0,10.0, place the scale inhibition performance of measuring medicament behind 80 ℃ the water bath with thermostatic control heating 10h then.PH less than 8.5 situation under, Scale inhibitors all has excellent adaptability.The result as shown in Figure 2.
Embodiment 4:
The present invention is used for the surface analysis of lime carbonate crystalline form
The crystal morphology of observing according to SEM, crystalline form that can qualitative definite lime carbonate.Can find the CaCO that Fig. 3 a produces when not adding Scale inhibitors from stereoscan photograph
3Crystal boundary has square geometry clearly, and smooth surface, shape are regular, and structure is tight.When adding polyaspartic acid scale inhibitor Fig. 3 b of modification, very big variation has taken place again in its exterior appearance, and outward appearance is bigger flats, and the edge is slick and sly, and it is long-pending that no obvious edges and corners, surperficial major part are uniform wadding water-water reactor, some bigger volumes are also arranged, do not have the cavity.The crystalline appearance is that when not having Scale inhibitors to exist, what lime carbonate formed is the single configuration of calcite, so form hard-packed bulk calcite precipitation easily in crystallisation process by the internal structure decision of itself.And when the poly aspartic acid of modification exists, formation be the mixed precipitation of calcite, two kinds of crystal formations of vaterite.In this case, because the participation of the polyaspartic acid scale inhibitor of modification, and different crystal forms hindered and damaged the original growth pattern of crystal mutually, so crystal particle volume is less, and deposit seeds does not have regular pattern.
More than disclosed only be specific embodiments of the invention; though the present invention discloses as above with preferred embodiment; but the present invention is not limited thereto; any those skilled in the art can think variation; in not breaking away from design philosophy of the present invention and scope; the present invention is carried out various changes and retouching, all should drop within protection scope of the present invention.
Claims (2)
1. the preparation method of a modified polyaspartic acid scale inhibitor is characterized in that, described method comprises the steps:
A. prepare polysuccinimide (PSI)
1. add 29-30g maleic anhydride and 55-65mL deionized water and stirring in the container, being warming up to and dripping massfraction after 80-90 ℃ is 25% ammoniacal liquor 45mL, obtains colourless solution after ammoniacal liquor dropwises, under 75-85 ℃, stirred 2 hours, suspended substance is dissolved fully, obtain clarifying homogeneous phase solution;
2. the homogeneous phase solution that 1. step is made is 90 ℃ of following underpressure distillation, obtain the mixture of white crystal and a small amount of thick liquid, add that to be heated to dissolution of crystals once more behind the 40-45mL deionized water be liquid in the mixture, this liquid is cooled off in ice bath, have crystal to separate out through cooling, suction filtration obtains white plates crystal maleimide;
3. the white plates crystal maleimide that 2. step is made adds the 20-30ml deionized water dissolving, is placed on methyl-silicone oil oil bath generation condensation reaction and obtains brown solid, is polysuccinimide;
B. the preparation of modified polyaspartic acid
1/2 of the polysuccinimide quality that 3. step is made is packed in the there-necked flask, add N according to the 1g/5mL volume, the N solvent dimethylformamide, in solvent, add the 1g thiocarbamide, normal temperature is used magnetic stirrer 1.5 hours down, obtain blood red clear solution, the sodium hydroxide solution that in blood red clear solution, adds 3mol/L, hydrolysis is 1 hour in 50 ℃ water bath with thermostatic control, solution is splashed in the beaker that adds 3-4 times of volume of ethanol at last, and under the situation of magnetic agitation, make it to precipitate, get the thick thing of reddish-brown, remove supernatant liquid, dry under the infrared drying lamp, finally obtain faint yellow end product modified polyaspartic acid scale inhibitor, the airtight preservation of porphyrize is standby.
2. the application method of a modified polyaspartic acid scale inhibitor that makes with the described preparation method of claim 1 is characterized in that, described modified polyaspartic acid scale inhibitor is 50～80 ℃ of temperature, and the pH value is to use in 6.0～8.5 the scope.
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| CN103113584A (en) * | 2013-02-28 | 2013-05-22 | 赵金姝 | Three compound combination flooding adopted environment-friendly preparation method of polyaspartic acid for oil field |
| CN104231267B (en) * | 2014-09-05 | 2017-05-31 | 武汉理工大学 | A kind of preparation of modified polyaspartic acid scale inhibitor and its application process |
| CN109970915B (en) * | 2017-12-28 | 2021-11-02 | 中国石油天然气股份有限公司 | Scale inhibitor and preparation method and application thereof |
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| CN108383251B (en) * | 2018-04-17 | 2021-07-16 | 唐山师范学院 | Preparation method of scale inhibitor |
| CN108975524A (en) * | 2018-07-05 | 2018-12-11 | 吕莉 | A kind of preparation method of anti-incrustation corrosion inhibitor |
| CN109019887B (en) * | 2018-08-24 | 2021-05-18 | 兰州交通大学 | Ecological water treatment chemical with corrosion and scale inhibition performance |
| CN109161019B (en) * | 2018-08-24 | 2021-02-05 | 兰州交通大学 | Preparation method of beta-dicarbonyl compound modified polyaspartic acid |
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| CN112246232A (en) * | 2020-10-16 | 2021-01-22 | 李艳艳 | Polyaspartic acid modified cellulose aerogel and preparation method thereof |
| CN112239276A (en) * | 2020-10-24 | 2021-01-19 | 山东普尼奥水处理有限公司 | Preparation method of non-phosphorus reverse osmosis scale inhibitor |
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| US5948748A (en) * | 1996-10-08 | 1999-09-07 | Kao Corporation | Detergent composition |
| CN101293945A (en) * | 2007-04-27 | 2008-10-29 | 四川中物凯沃科技有限公司 | Method for preparing modified poly-epoxy succinic acid derivative |
| CN101665553A (en) * | 2009-07-30 | 2010-03-10 | 中国工程物理研究院化工材料研究所 | Preparation method of polyepoxysuccinate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654159A (en) * | 1985-06-24 | 1987-03-31 | The Procter & Gamble Company | Ether hydroxypolycarboxylate detergency builders |
| US5948748A (en) * | 1996-10-08 | 1999-09-07 | Kao Corporation | Detergent composition |
| CN101293945A (en) * | 2007-04-27 | 2008-10-29 | 四川中物凯沃科技有限公司 | Method for preparing modified poly-epoxy succinic acid derivative |
| CN101665553A (en) * | 2009-07-30 | 2010-03-10 | 中国工程物理研究院化工材料研究所 | Preparation method of polyepoxysuccinate |
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