CN108862642A - The preparation method of modified polyaspartic acid scale inhibitor - Google Patents
The preparation method of modified polyaspartic acid scale inhibitor Download PDFInfo
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- CN108862642A CN108862642A CN201810689782.2A CN201810689782A CN108862642A CN 108862642 A CN108862642 A CN 108862642A CN 201810689782 A CN201810689782 A CN 201810689782A CN 108862642 A CN108862642 A CN 108862642A
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- acid
- added
- scale inhibitor
- modified polyaspartic
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention proposes a kind of preparation methods of modified polyaspartic acid scale inhibitor, include the following steps：1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then in 106~110 DEG C of progress amination hydrolysis, it is cooled to room temperature, adds sodium bisulfate catalysis agent, react to obtain polysuccinimide under 120~135 DEG C of vacuum conditions in mixing sour solvent of the sulfuric acid with hydrochloric acid；2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid is added with oxalic acid and reacts 1.5~2.5h in 100~110 DEG C in oil bath pan, it is cooling, dehydrated alcohol washing, drying is added, obtains final product modified polyaspartic acid.The antisludging agent has good scale-inhibiting properties to calcium carbonate and calcium phosphate, introduces carboxylic acid group and sulfonic group, improves the comprehensive performance of its antiscaling dispersion, and have good corrosion inhibition and biodegradability.
Description
Technical field
The invention belongs to antisludging agent technical fields, and in particular to a kind of preparation method of modified polyaspartic acid scale inhibitor.
Background technique
Currently, the predicament that the use of conventional energy resource such as coal, oil and natural gas is faced with resource exhaustion, pollutes environment.
Geothermal energy belongs to China《Renewable Energy Law》The renewable new energy type that (2006) are included in, generally by pumping underground hot water
And utilize, it is one of energy conservation, the effective way of emission reduction.But the fouling of GEOTHERMAL WATER must face in geothermal energy application
One problem.Being handled using antisludging agent GEOTHERMAL WATER is still currently employed main means.
Poly-aspartate is a kind of novel biodegradable environmentally friendly high molecular material, and raw material is easy to get, valence
Lattice are not high, are widely used for water treatment agent, detergent, cosmetics, bacteriostatic agent, dispersing agent, chelating agent, pesticide, agricultural in recent years
The fields such as chemical fertilizer.Due to the feature on poly-aspartate molecular structure, easily with adsorption of metal ions or combination, therefore have prevent
The effect of scale.Poly-aspartate is because having good biocompatibility and not phosphorous, it has also become heat studied both at home and abroad at present
Point, but scale-inhibiting properties to calcium carbonate, calcium phosphate and dispersibility are not so good as now widely used acrylic acid in any case
With Malaysia acids polymers, its application is made to receive certain limitation.Chinese patent CN101792504B has invented a kind of modification
Maleic anhydride is reacted with ammonia water obtained maleimide by the preparation of polyaspartic acid scale inhibitor and application method, by contracting
Poly- reaction generates polysuccinimide, and N-N- dimethylformamide and thiocarbamide is being added, then is hydrolyzed in the presence of a base modified poly-
Aspartic acid antisludging agent, modified polyaspartic acid have good scale-inhibiting properties to calcium carbonate, but especially for other dirty matter
Relatively common calcium phosphate scale-inhibiting properties are poor, therefore poly-aspartate is further modified to enhance it to various in recent years
The scale-inhibiting properties of dirty matter.
Summary of the invention
The present invention proposes a kind of modified polyaspartic acid scale inhibitor, which has well calcium carbonate and calcium phosphate
Scale-inhibiting properties introduce carboxylic acid group and sulfonic group, improve the comprehensive performance of its antiscaling dispersion, and have good corrosion inhibition
And biodegradability.
The technical proposal of the invention is realized in this way：
A kind of preparation method of modified polyaspartic acid scale inhibitor, includes the following steps：
1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then
It in 106~110 DEG C of progress amination hydrolysis, is cooled to room temperature, adds sodium bisulfate catalysis agent, in the mixed of sulfuric acid and hydrochloric acid
It closes to react under 120~135 DEG C of vacuum conditions in sour solvent and obtains polysuccinimide；
2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid and oxalic acid is added in oil
1.5~2.5h is reacted in bath in 100~110 DEG C, it is cooling, dehydrated alcohol washing, drying is added, it is modified poly- to obtain final product
Aspartic acid.
Further, the ratio between sulfuric acid and the volume of the hydrochloric acid described in the mixing sour solvent are 1~1.5:1.
Further, the concentration of the sulfuric acid is 10~15mol/L, and the concentration of the hydrochloric acid is 5~8mol/L.
Further, the molar ratio of the polysuccinimide, the lignin sulfonic acid and the oxalic acid is 1:0.8~1.2:
0.2~0.5.
Further, the step 2) further includes adding in the system after reacting poly- succinamide with oxalic acid with lignin sulfonic acid
Enter after alkali adjusts pH to 8~10,40~60 DEG C of 30~50min of hydrolysis and adds dehydrated alcohol washing.
Beneficial effects of the present invention：
The preparation method of modified polyaspartic acid scale inhibitor of the invention, the polysuccinimide being prepared are with two
First sulfoxide is solvent and catalyst of the oxalic acid as lignin sulfonic acid, without using the thiocarbamide with carcinogenicity as catalysis
Agent improves the synthesis of its antiscaling dispersion so that the modified polyaspartic acid finally obtained contains sulfonic acid group and carboxylic acid group
Performance, and there is good corrosion inhibition and biodegradability, do not have to worry carcinogenic etc. be unfavorable for applied to recirculated cooling water
It influences.
Modified polyaspartic acid scale inhibitor prepared by the present invention is nontoxic, without phosphorus, does not destroy natural ecological environment, has resistance
Dirt, inhibition and biodegradable performance can be improved poly-aspartate to the scale-inhibiting properties of calcium carbonate and calcium phosphate, obtaining height
The advantages that while imitating scale inhibition efficiency, with low production cost, nontoxic to environment, scale inhibition is high-efficient, biodegradable.
Prepared modified polyaspartic acid scale inhibitor usage amount of the invention is that 5~15mg is added in every 1 liter of water.
Specific embodiment
Embodiment 1
A kind of preparation method of modified polyaspartic acid scale inhibitor, includes the following steps：
1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then
In 108 DEG C of progress amination hydrolysis, it is cooled to room temperature, adds sodium bisulfate catalysis agent, in the mixed acid of sulfuric acid and hydrochloric acid
Reaction obtains polysuccinimide under 125 DEG C of vacuum conditions in solvent；Sulfuric acid described in the mixing sour solvent and the salt
The ratio between volume of acid is 1.2:1；The concentration of sulfuric acid is 12mol/L, and the concentration of the hydrochloric acid is 7mol/L
2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid and oxalic acid is added in oil
2h is reacted in 105 DEG C in bath, it is cooling, alkali is added and adjusts pH to 9,50 DEG C of hydrolysis 40min, dehydrated alcohol is added and washs, is dry,
Obtain final product modified polyaspartic acid.The molar ratio of polysuccinimide, the lignin sulfonic acid and the oxalic acid is 1:
1:0.3。
Embodiment 2
A kind of preparation method of modified polyaspartic acid scale inhibitor, includes the following steps：
1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then
In 106 DEG C of progress amination hydrolysis, it is cooled to room temperature, adds sodium bisulfate catalysis agent, in the mixed acid of sulfuric acid and hydrochloric acid
Reaction obtains polysuccinimide under 135 DEG C of vacuum conditions in solvent；Mix sulfuric acid described in sour solvent and the hydrochloric acid
The ratio between volume is 1:1；The concentration of sulfuric acid is 10mol/L, and the concentration of hydrochloric acid is 8mol/L.
2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid and oxalic acid is added in oil
2.5h is reacted in 100 DEG C in bath, it is cooling, alkali is added and adjusts pH to 8,40 DEG C of hydrolysis 50min, dehydrated alcohol is added and washs, is dry
It is dry, obtain final product modified polyaspartic acid.Polysuccinimide, the lignin sulfonic acid and the oxalic acid molar ratio be
1:0.8.2:0.5。
Embodiment 3
A kind of preparation method of modified polyaspartic acid scale inhibitor, includes the following steps：
1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then
In 110 DEG C of progress amination hydrolysis, it is cooled to room temperature, adds sodium bisulfate catalysis agent, in the mixed acid of sulfuric acid and hydrochloric acid
Reaction obtains polysuccinimide under 120 DEG C of vacuum conditions in solvent；Mix sulfuric acid described in sour solvent and the hydrochloric acid
The ratio between volume is 1.5:1；The concentration of sulfuric acid is 15mol/L, and the concentration of hydrochloric acid is 5mol/L.
2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid and oxalic acid is added in oil
1.5h is reacted in 110 DEG C in bath, it is cooling, alkali is added and adjusts pH to 10,60 DEG C of hydrolysis 30min, dehydrated alcohol is added and washs, is dry
It is dry, obtain final product modified polyaspartic acid.The molar ratio of polysuccinimide, lignin sulfonic acid and oxalic acid is 1:1.2:
0.2。
Test example 1
Water sampling (the Ca containing 320mg/L2+, the phosphate radical of 8mg/L and the bicarbonate radical of 450mg/L) embodiment 1 to 3 is added
The modified polyaspartic acid scale inhibitor 10mg/L being prepared, control pH value are 7, and water-bath 6h, cold in 80 DEG C of thermostat water baths
But to its scale inhibition performance is surveyed after room temperature, the poly-aspartate 10mg/L of unmodified processing, the result of measurement such as 1 institute of table is added in control group
Show.
Table 1
| Project experimental group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Control group |
| Scale inhibition performance | 95.3% | 94.2% | 96.7% | 83.8% |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of modified polyaspartic acid scale inhibitor, which is characterized in that include the following steps：
1) configuration of maleic anhydride aqueous solution：It is added drop-wise to after urea is dissolved in water in the aqueous solution of maleic anhydride, then in 106
~110 DEG C of progress amination hydrolysis, are cooled to room temperature, add sodium bisulfate catalysis agent, in the mixed acid of sulfuric acid and hydrochloric acid
Reaction obtains polysuccinimide under 120~135 DEG C of vacuum conditions in solvent；
2) after polysuccinimide being taken out cooling, using dimethyl sulfoxide as solvent, lignin sulfonic acid and oxalic acid is added in oil bath pan
In 1.5~2.5h is reacted in 100~110 DEG C, it is cooling, dehydrated alcohol washing, dry is added, obtains the modified poly- asparagus fern of final product
Propylhomoserin.
2. the preparation method of modified polyaspartic acid scale inhibitor according to claim 1, which is characterized in that the mixed acid
The ratio between volume of sulfuric acid described in solvent and the hydrochloric acid is 1~1.5:1.
3. the preparation method of modified polyaspartic acid scale inhibitor according to claim 2, which is characterized in that the sulfuric acid
Concentration is 10~15mol/L, and the concentration of the hydrochloric acid is 5~8mol/L.
4. the preparation method of modified polyaspartic acid scale inhibitor according to claim 1, which is characterized in that the poly- amber
The molar ratio of acid imide, the lignin sulfonic acid and the oxalic acid is 1:0.8~1.2:0.2~0.5.
5. the preparation method of modified polyaspartic acid scale inhibitor according to claim 1, which is characterized in that the step 2)
It further include that alkali adjusting pH to 8~10 is added in the system after reacting poly- succinamide with oxalic acid with lignin sulfonic acid, 40~60
DEG C hydrolysis 30~50min after add dehydrated alcohol washing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607832A (en) * | 2018-11-30 | 2019-04-12 | 中能化地大热能(湖北)有限责任公司 | A kind of polyaspartic acid scale inhibitor and preparation method thereof |
| CN111777200A (en) * | 2020-07-17 | 2020-10-16 | 陕西津阳水处理股份有限公司 | Scale and corrosion inhibitor for water treatment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884141A (en) * | 2006-07-05 | 2006-12-27 | 太原理工大学 | Biodegradable composite corrosion and scale inhibitor and method for preparing same |
| US20110213099A1 (en) * | 2007-09-25 | 2011-09-01 | Patil Damodar R | Method of making graft copolymers from sodium poly(aspartate) and the resulting graft copolymer |
| CN104231267A (en) * | 2014-09-05 | 2014-12-24 | 武汉理工大学 | Preparation method and application method of modified polyaspartic acid scale inhibitor |
| CN104556431A (en) * | 2013-10-29 | 2015-04-29 | 程池 | Preparation method of modified polyaspartic acid scale inhibitor |
-
2018
- 2018-06-28 CN CN201810689782.2A patent/CN108862642A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884141A (en) * | 2006-07-05 | 2006-12-27 | 太原理工大学 | Biodegradable composite corrosion and scale inhibitor and method for preparing same |
| US20110213099A1 (en) * | 2007-09-25 | 2011-09-01 | Patil Damodar R | Method of making graft copolymers from sodium poly(aspartate) and the resulting graft copolymer |
| CN104556431A (en) * | 2013-10-29 | 2015-04-29 | 程池 | Preparation method of modified polyaspartic acid scale inhibitor |
| CN104231267A (en) * | 2014-09-05 | 2014-12-24 | 武汉理工大学 | Preparation method and application method of modified polyaspartic acid scale inhibitor |
Non-Patent Citations (1)
| Title |
|---|
| 刘欣 等: ""聚天冬氨酸与木质素磺酸钠复配物对碳酸钙阻垢性能的研究"", 《化学研究与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607832A (en) * | 2018-11-30 | 2019-04-12 | 中能化地大热能(湖北)有限责任公司 | A kind of polyaspartic acid scale inhibitor and preparation method thereof |
| CN111777200A (en) * | 2020-07-17 | 2020-10-16 | 陕西津阳水处理股份有限公司 | Scale and corrosion inhibitor for water treatment |
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