CN1318477C - Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid - Google Patents
Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid Download PDFInfo
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- CN1318477C CN1318477C CNB2004100158755A CN200410015875A CN1318477C CN 1318477 C CN1318477 C CN 1318477C CN B2004100158755 A CNB2004100158755 A CN B2004100158755A CN 200410015875 A CN200410015875 A CN 200410015875A CN 1318477 C CN1318477 C CN 1318477C
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Abstract
The present invention belongs to the technical field of chemical industry, particularly to a method for preparing a biodegradable corrosion-scale inhibitor-poly-aspartic acid. In the present invention, after maleic anhydride is converted into maleic amine, a dry substance of the maleic amine is prepared via a spray dryer; then, the dry substance is condensed into poly-succinimide; finally, the poly-succinimide is hydrolyzed into the poly-aspartic acid under the existence of alkali. The present invention is a homopolymer containing amide groups and carboxyl, has favorable scale inhibition and dispersion capability to multiple kinds of scale, and has favorable corrosion inhibition performance. The present invention can be widely applied to the aspects of circulating cooling water systems, boiler water, oil-field water, seawater desalination, etc.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method of biodegradable corrosion inhibiting and descaling agent poly aspartic acid, this corrosion inhibiting and descaling agent is a kind of without phosphorus low-molecular-weight homopolymer, belong to phosphorus-free green environment-friendly type, biodegradable corrosion inhibiting and descaling agent, the scale inhibition and the inhibition that are used for water quality are handled.
Background technology
In relating to the every field of water treatment, fouling and corrosion all can bring serious consequence to production, reduce throughput, even cause shut-down.As in industrial circulating cooling water system, CaCO
3Be that the most common dirt usually causes the fouling of equipment pipe internal surface, influence flowing and heat transfer efficiency of water, serious also can cause line clogging, causes shut-down, and corrosion then causes severe impairment to equipment and pipeline, reduces normal work-ing life.In paper industry, CaCO
3, BaSO
4Be pulp digester, give birth to the liquid pipeline, drift dirt common in device and the extraction element, the formation of these dirts increases steam consumption, reduction is given birth to liquid and flowed, increases the saltcake loss ducted, and then reduction quality product and throughput.In petroleum industry, CaCO
3, CaSO
4, BaSO
4Be the main component of dirt, can cause the decline of throughput.In the saturating desalination of seawater reverse osmosis, CaSO
4, BaSO
4, SrSO
4Be the main component of dirt, these dirts can stop up film, cause that membrane flux reduces, and throughput descends, and membrane lifetime shortens, and increases production cost, and serious also can causing produced and stopped work.Therefore the processing of the scale inhibition of service water is the research topic that people paid close attention to always.Utilization adds Scale inhibitors, and to carry out that scale inhibition handles be convenient relatively in numerous method of scale inhibition and a kind of method efficiently.
Phosphorus line formulation accounts for very big proportion in the corrosion inhibiting and descaling agent of China at present, raising along with human environmental consciousness, environmental regulation is further strict, many countries have begun the discharging of phosphorus restriction, promoted developing rapidly of low-phosphorous, without phosphorus prescription, low-phosphorous, without phosphorus green water conditioner has become the hot subject of domestic and international water conditioner development aspect.
United States Patent (USP) US4 in the existing technology, 839,461 have proposed a kind of preparation method who prepares poly aspartic acid, in the water-soluble solution of maleic anhydride, pass through dropping ammonia, change the amine salt of toxilic acid into, the direct heat polycondensation is hydrolyzed under the effect of sodium hydroxide and is polymerized to poly aspartic acid for poly-succinimide under 125 ℃ then～145 ℃ the temperature.US5,296,578 bring up to 220 ℃～260 ℃ with the temperature of thermal polycondensation in the above-mentioned reaction, to improve the productive rate of poly-succinimide.US5,714,558 to be reported in the pressurized vessel with water or organic solvent be medium, add maleic anhydride and gaseous ammonia, be warming up to 130 ℃～300 ℃, reacted 5 minutes～5 hours, generate poly-succinimide, if with water be solvent then direct hydrolysis be poly aspartic acid, if be that solvent then needs organic solvent is isolated, and then be hydrolyzed to poly aspartic acid with the organic solvent.The mass treatment that technological process produces very, and equipment requirements is high.
Chinese patent CN 1398799A is hydrolyzed to toxilic acid with it, generate the amine salt of toxilic acid then with the ammoniacal liquor reaction, the amine salt of toxilic acid is carried out thermal polycondensation at a certain temperature obtain poly-succinic diamide, separate drying and go out poly-succinic diamide, cyclodehydration generates polysuccinimide at a certain temperature again, at last the sodium salt of hydrolysis poly aspartic acid under the effect of aqueous sodium hydroxide solution.Also there is not preparation method's report at present about biodegradable corrosion inhibiting and descaling agent poly aspartic acid.
Summary of the invention
Purpose of the present invention aims to provide the preparation method of a kind of processing step weak point, art breading convenience, the simple scale inhibitor poly-asparagic acid of equipment.
The preparation method of the biodegradable corrosion inhibiting and descaling agent poly aspartic acid that the present invention proposes, be to be raw material with the maleic anhydride, generate toxilic acid through basic hydrolysis, drying handle the Malaysia acid amide, carry out polyreaction again and generate polysuccinimide, at last the sodium salt of hydrolysis generation poly aspartic acid under the alkali existence condition.Concrete steps are: at first maleic anhydride is hydrolyzed to toxilic acid, then with its cooling, control reaction temperature is 0-20 ℃, adds 25% ammoniacal liquor, generates the aqueous solution of Malaysia acid amide; The aqueous solution with the Malaysia acid amide obtains white Malaysia acid amide by the spray-dryer drying then, and temperature is controlled at 120 ℃～180 ℃; Place pressurized vessel to carry out polycondensation exsiccant Malaysia acid amide, temperature is controlled at 200 ℃～240 ℃, and the reaction times is 3～5 hours, and pressure is 0.4～0.6MPa, obtains polysuccinimide; With the hydrolysis of polysuccinimide hydro-oxidation sodium water solution, control reaction temperature is 70 ℃～90 ℃ then, gets the poly aspartic acid solution of the sticking shape of reddish-brown, and the size of its solid content can be regulated by the content of control water.
Among the present invention, toxilic acid and ammonia (25%wt. ammoniacal liquor) mol ratio is 1: 1.2～1: 2.
Among the present invention, the mol ratio of poly-succinimide and sodium hydroxide is 1: 1～1: 1.2.
U.S. Pat 4,839, be in the technological process of polysuccinimide at Malaysia acid amide thermal polycondensation in 461 and US5,296,578, owing to be that the aqueous solution is carried out polymerization earlier, slowly dehydration is for polysuccinimide again, so technology begins easily to produce foaming, the extremely difficult thick material that stirs, produce again afterwards attached to the hard solid state material on the equipment, thereby it is make it handle very trouble, and high to equipment requirements.And the present invention comes out the Malaysia acid amide by the spray-dryer drying, places pressurized vessel to carry out thermal polycondensation again, has avoided occurring the extremely difficult thick material that stirs owing to carry out polycondensation under anhydrous state, and attached to the hard solid state material on the equipment.
Because the Malaysia acid amide is directly placed pressurized vessel, by control pressure polymerization, dehydration are carried out synchronously among the present invention, technology, equipment are more simple, and technological process and process time all shorten greatly.
The present invention is to CaCO
3, CaSO
4, BaSO
4, SrSO
4Good scale inhibition effect is arranged, especially calcium is had very high tolerance, chlorine and iron ion are had tangible stability, and very strong thermotolerance is arranged, can be widely used in aspects such as recirculating cooling water system, feedwater, oil-field water, sea water desalinization.
Embodiment
Further describe the present invention below by a series of embodiment.
Embodiment 1:
In the three-necked flask of being furnished with stirring, thermometer, add the 196g maleic anhydride, add 98ml water again, in water-bath, be heated to 55 ℃～80 ℃ then, stirred 30 minutes maleic anhydride dissolving back, be cooled to again about 5 ℃, stop to stir, slowly add 25% ammonia soln 272g.This liquid is dry in spray-dryer, 160 ℃ of temperature white Malaysia acid amide, then the Malaysia acid amide is placed pressurized vessel to stir and is heated to about 220 ℃ with oil bath, pressure maintains 0.4MPa, react 5 hours, must polysuccinimide.Polysuccinimide under 50 ℃～80 ℃ condition, is added the sodium salt that 20% aqueous sodium hydroxide solution is hydrolyzed to poly aspartic acid, solid content be not less than 35% the sticking shape liquid of reddish-brown, promptly get poly aspartic acid solution.
Embodiment 2:
In the three-necked flask of being furnished with stirring, thermometer, add the 196g maleic anhydride, add 98ml water again, in water-bath, be heated to 55 ℃～80 ℃ then, stirred 30 minutes maleic anhydride dissolving back, be cooled to again about 5 ℃, stop to stir, slowly add 25% ammonia soln 163g, generate the Malaysia acid amide.With this Malaysia acid amide liquid dry white Malaysia acid amide in 160 ℃ spray-dryer, then the Malaysia acid amide is placed pressurized vessel to stir and be heated to about 240 ℃ with oil bath,, pressure maintains 0.5MPa,, react 4 hours, must polysuccinimide.Be cooled to 50 ℃～80 ℃, add the sodium salt that 20% aqueous sodium hydroxide solution is hydrolyzed to poly aspartic acid, solid content be not less than 35% the sticking shape liquid of reddish-brown, promptly get poly aspartic acid solution.
Embodiment 3:
In the three-necked flask of being furnished with stirring, thermometer, add the 294g maleic anhydride, add 140ml water again, in water-bath, be heated to 55 ℃～80 ℃ then, stirred 30 minutes maleic anhydride dissolving back, be cooled to again about 5 ℃, stop to stir, slowly add 25% ammonia soln 306g, generate the Malaysia acid amide.With this Malaysia acid amide liquid dry white Malaysia acid amide in 160 ℃ spray-dryer, then the Malaysia acid amide is placed pressurized vessel to stir and be heated to about 230 ℃ with oil bath, pressure maintains 0.5MPa, react 3 hours, must polysuccinimide.Be cooled to 50 ℃～80 ℃, add the sodium salt that 20% aqueous sodium hydroxide solution is hydrolyzed to poly aspartic acid, solid content be not less than 35% the sticking shape liquid of reddish-brown, promptly get poly aspartic acid solution.
Embodiment 4:
In the three-necked flask of being furnished with stirring, thermometer, add the 294g maleic anhydride, add 140ml water again, in water-bath, be heated to 55 ℃～80 ℃ then, stirred 30 minutes maleic anhydride dissolving back, be cooled to again about 5 ℃, stop to stir, slowly add 25% ammonia soln 245g, generate the Malaysia acid amide.With this Malaysia acid amide liquid dry white Malaysia acid amide in 170 ℃ spray-dryer, then the Malaysia acid amide is placed pressurized vessel to stir and be heated to about 200 ℃ with oil bath,, pressure maintains 0.4MPa, react 5 hours, must polysuccinimide.Be cooled to 50 ℃～80 ℃, add the sodium salt that 20% aqueous sodium hydroxide solution is hydrolyzed to poly aspartic acid, solid content be not less than 35% the sticking shape liquid of reddish-brown, promptly get poly aspartic acid solution.
Claims (3)
1, a kind of preparation method of biodegradable corrosion inhibiting and descaling agent poly aspartic acid, it is characterized in that concrete steps are: at first maleic anhydride is hydrolyzed to toxilic acid, then with its cooling, control reaction temperature is 0-20 ℃, the ammoniacal liquor of adding 25%, the aqueous solution of generation Malaysia acid amide; The aqueous solution with the Malaysia acid amide obtains white Malaysia acid amide by the spray-dryer drying then, and temperature is controlled at 120 ℃～180 ℃; Place pressurized vessel that polycondensation takes place exsiccant Malaysia acid amide, temperature is controlled at 200 ℃～240 ℃, and the reaction times is 3～5 hours, and pressure is 0.4～0.6MPa, obtains polysuccinimide; Then polysuccinimide is added 20% aqueous sodium hydroxide solution hydrolysis, control reaction temperature is 70 ℃～90 ℃, gets the poly aspartic acid solution of the sticking shape of reddish-brown.
2, the preparation method of biodegradable corrosion inhibiting and descaling agent poly aspartic acid according to claim 1, the mol ratio that it is characterized in that toxilic acid and ammoniacal liquor is 1: 1.2～1: 2.
3, the preparation method of biodegradable corrosion inhibiting and descaling agent poly aspartic acid according to claim 1, the mol ratio that it is characterized in that polysuccinimide and sodium hydroxide is 1: 1～1: 1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100158755A CN1318477C (en) | 2004-01-15 | 2004-01-15 | Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100158755A CN1318477C (en) | 2004-01-15 | 2004-01-15 | Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid |
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|---|---|
| CN1557857A CN1557857A (en) | 2004-12-29 |
| CN1318477C true CN1318477C (en) | 2007-05-30 |
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| CNB2004100158755A Expired - Fee Related CN1318477C (en) | 2004-01-15 | 2004-01-15 | Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768268B (en) * | 2010-02-11 | 2012-06-13 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
| US5219952A (en) * | 1992-09-18 | 1993-06-15 | Donlar Corporation | Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia |
| US5296578A (en) * | 1992-09-18 | 1994-03-22 | Donlar Corporation | Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia |
| US5543490A (en) * | 1992-12-24 | 1996-08-06 | Bayer Ag | Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof, and the use of these compounds |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
-
2004
- 2004-01-15 CN CNB2004100158755A patent/CN1318477C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
| US5219952A (en) * | 1992-09-18 | 1993-06-15 | Donlar Corporation | Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia |
| US5296578A (en) * | 1992-09-18 | 1994-03-22 | Donlar Corporation | Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia |
| US5543490A (en) * | 1992-12-24 | 1996-08-06 | Bayer Ag | Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof, and the use of these compounds |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
Non-Patent Citations (2)
| Title |
|---|
| 聚天冬氨酸制造工艺研究进展 杨士林，环境污染治理技术与设备，第3卷第9期 2002 * |
| 聚天冬氨酸的合成与阻垢缓蚀性能评述 徐二仓，江苏化工，第31卷第4期 2003 * |
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|---|---|
| CN1557857A (en) | 2004-12-29 |
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