CN101497481B - Scale inhibitor for reverse osmosis membrane and preparation thereof - Google Patents
Scale inhibitor for reverse osmosis membrane and preparation thereof Download PDFInfo
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- CN101497481B CN101497481B CN2009100802514A CN200910080251A CN101497481B CN 101497481 B CN101497481 B CN 101497481B CN 2009100802514 A CN2009100802514 A CN 2009100802514A CN 200910080251 A CN200910080251 A CN 200910080251A CN 101497481 B CN101497481 B CN 101497481B
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Abstract
The invention relates to a reverse osmosis water treatment agent, in particular to a scale inhibitor for reverse osmosis membrane. A formulation comprises organic poly-phosphate compound, phosphine carboxylic acid, crylic acid biopolymer, polymaleic acid compound and water; the compositions have the following weight mixture ratio: 1.0 to 6.0 percent of the organic poly-phosphate compound, 2 to 12 percent of the phosphine carboxylic acid, 10 to 40 percent of the crylic acid biopolymer, 0.2 to 2 percent of the polymaleic acid compound and the balance being water. The scale inhibitor for the reverse osmosis membrane utilizes synergism of each composition, improves the lower-limit scale inhibition performance of the scale inhibitor on reverse osmosis concentrated water (highly mineralized water), effectively controls large-scale formation on the reverse osmosis membrane of calcium, strontium, barium, magnesium, iron, copper, zinc and other salts, reduces the cleaning frequency of a reverse osmosis system and maintains normal water drainage and water supply pressure.
Description
Technical field
The present invention relates to the reverse osmosis membrane water technology, the water treatment scale agent that a kind of reverse osmosis membrane is used.
Background technology
Reverse osmosis technology is a kind of membrane separation technique, and the application in water treatment field is very extensive, can be except that a large amount of impurity in anhydrating by membrane sepn.For example inorganics, metal ion, organism, colloid, bacterium and virus etc. even are a kind of efficient, low consumption, pollution-free water treatment new technology.The ultrapure water of reverse osmosis membrane technology in industries such as chemical industry, medicine, food, electronics produced, obtained and widespread use in desalination, sewage disposal and the various product separation purifying technique process in recent years.
In the reverse osmosis water treatment process, it is an important factor that influences reverse osmosis system working efficiency and film work-ing life that film pollutes.In the reverse osmosis water treatment process, a large amount of dirt depositions can appear in the reverse osmosis membrane life-time service, cause the dirty stifled phenomenon of film, cause the reverse osmosis effect to descend, and will change reverse osmosis membrane at short notice when serious.People are to discussions that conduct a research of the dirty stifled cause of film, and the pollution of film can be divided into inorganic scale and organic deposition pollution.Can be divided into particle dirt and colloid dirt or microorganism dirt from the form of dirt, adopt flocculation agent flocculation sediment and filtration to solve for the particle dirt, microorganism dirt then adding of germicide solves, and inorganic scale then adopts the way that adds Scale inhibitors to solve.Well behaved Scale inhibitors can suppress the formation of dirt, prolongs the work-ing life of reverse osmosis membrane, thereby reduces the running cost of reverse osmosis system.At present, domestic reverse osmosis antisludging agent research and application are being carried out always, reach desired level far away, and the reverse osmosis antisludging agent kind differs in the market, the product scale-inhibiting properties is not high, and its scale inhibition efficient does not reach scale inhibition efficient (90%) level of import reverse osmosis antisludging agent as yet.
Summary of the invention
The present invention aims to provide the Scale inhibitors that a kind of new reverse osmosis membrane is used, to reach higher scale inhibition efficient.
Purpose of the present invention is achieved through the following technical solutions:
The Scale inhibitors that provides a kind of reverse osmosis membrane to use, its component comprises organic multicomponent phosphinic acid compounds, phosphine carboxylic acid, vinylformic acid copolymer and polymaleic acid compound and water, the weight percent of each component is an organic multicomponent phosphonate compounds 1.0～6.0%, phosphine carboxylic acid 2～12%, vinylformic acid copolymer 10～40%, polymaleic acid 0.2～2%, all the other are water.
Prescription is organic multicomponent phosphinic acid compounds 1.2～4.8% preferably, phosphine carboxylic acid 4～10%, and vinylformic acid copolymer 16～32%, polymaleic acid 0.4～1.6%, all the other are water.
Best prescription is an organic multicomponent phosphinic acid compounds 1.5～4%, phosphine carboxylic acid 6～8%, and vinylformic acid copolymer 16～32%, polymaleic acid 0.6～1.2%, all the other are water.
Described organic multicomponent phosphinic acid compounds comprises 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP); Use 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP) preferably; The best is selected 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) for use.
Described phosphine carboxylic acid comprises 2-phosphono-1,2,4-butane tricarboxylate (PBTCA), 2-HPAA (HPAA), polyamino polyether base methylenephosphonic acid salt (PAPEMP); Select 2-phosphono-1,2 preferably for use, 4-butane tricarboxylate (PBTCA) and 2-HPAA (HPAA); Preferably use 2-phosphono-1,2,4-butane tricarboxylate (PBTCA).
The vinylformic acid copolymer is a kind of in vinylformic acid/Propylene glycol monoacrylate, vinylformic acid/methyl acrylate, vinylformic acid/styrene sulfonic acid, the vinylformic acid/itaconic acid copolymer; Select vinylformic acid/Propylene glycol monoacrylate or vinylformic acid/methyl acrylate copolymer preferably for use; The best is selected vinylformic acid/methyl acrylate copolymer for use.
The preparation method of Scale inhibitors of the present invention is: the water, organic multicomponent phosphonate, phosphine carboxylic acid, vinylformic acid copolymer and the polymaleic acid that add described ratio in container successively, stirring and dissolving, acid or alkali with routine are regulated pH value to 1.5～3.5, and the liquid that obtains is Scale inhibitors of the present invention.
Reverse osmosis membrane antisludging agent of the present invention is a liquid, dissolves each other with any ratio of water.Adding dose is 1～10mg/L with the ratio of giving water inventory, and the best is 2～8mg/L, and specifically adding dose should regulate according to additional change of water quality.Because it is acid that Scale inhibitors of the present invention is, the medicine machine material should adopt acid resisting material, for example chemical industry equipment and the tubing made of stainless steel or plastics.
Compared with prior art, antisludging agent for osmosis-reverse membrane of the present invention has following beneficial effect:
1. has higher scale-inhibiting properties.
Reverse osmosis membrane antisludging agent of the present invention utilizes the synergistic function of its each component, improve the lower bound scale-inhibiting properties of Scale inhibitors to reverse osmosis concentrated water (concentrated water), scale inhibition performance can reach more than 95%, can effectively control the extensive fouling on reverse osmosis membrane of salts such as calcium, strontium, barium, magnesium, iron, copper, zinc, reduce the reverse osmosis system cleaning frequency, safeguard normal water-flowing amount and feed pressure.
2. applied widely
Reverse osmosis membrane antisludging agent of the present invention is applicable to multiple class reverse osmosis membranes such as cellulose acetate membrane, composite membrane.
3. Scale inhibitors of the present invention also is applicable to the various water ph values of giving, and need not during use to regulate to water ph value; Reverse osmosis membrane is not damaged, pollution-free, be the Scale inhibitors of a kind of reverse osmosis system safely and efficiently special use.
Embodiment
Below use Examples set the present invention, but example does not limit to its scope.
Example 1.
The Scale inhibitors prescription:
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 3%
2-phosphono-1,2,4-butane tricarboxylate (PBTCA) 7%
Vinylformic acid/methyl acrylate copolymer 20%
Polymaleic acid 1%
Water 69%
The static reverse osmosis antisludging agent test water quality of estimating:
Ca
2+100mg/L HCO
3 -100mg/L pH value 8.6
Antisludging test temperature: 80 ℃ ± 1 ℃
Time of repose: 10 hours
Added amount of chemical: 5mg/L
Lime carbonate scale inhibition performance: 95.2%
Example 2.
The Scale inhibitors prescription:
Amino Trimethylene Phosphonic Acid (ATMP) 2.5%
2-phosphono-1,2,4-butane tricarboxylate (PBTCA) 6.5%
Vinylformic acid/Propylene glycol monoacrylate multipolymer 21%
Polymaleic acid 1%
Water 69%
Compound back such as the flocculation agent that Scale inhibitors of the present invention and reverse osmosis system add, reductive agent, sterilant forms clear solution, puts for a long time not become muddy.This Scale inhibitors is carried out static composite scale test, and carries out antisludging test relatively, result such as following table in single agent use with this Scale inhibitors:
Data declaration in the table, the Scale inhibitors in the example 2 is in the presence of flocculation agent, reductive agent, sterilant, and its scale inhibition performance is similar substantially, and Scale inhibitors of the present invention has sufficient compatibility and high anti-interfering performance.
Example 3.
The Scale inhibitors prescription is with example 1
On the reverse osmosis equipment of 100 tons/hour of certain company's processing water yields, move adding consistency 5mg/L.
Influent quality:
Na
+ 395mg/L HCO
3 - 340mg/L
Ca
2+ 7.00mg/L Cl
- 80.0mg/L
Mg
2+ 13.5mg/L SO
4 2- 86.50mg/L
Fe
3+ 0.30mg/L CO
3 2+ 20mg/L
AL
3+ 0.15mg/L SDI ＜3
SiO
2 2- 20.0mg/L COD
Mn 1.5mg/L
Total hardness 25mg/L PH 8.70
Move 10 months, two sections pressure reduction of reverse osmosis membrane are reduced to 0.09 MPa from 0.14 MPa, and ratio of desalinization remains on more than 98.5%, and water purification output 8.5% cleaning interval that descended extended to 10 months from original 2.5 months～3 months.
Claims (10)
1. an antisludging agent for osmosis-reverse membrane is characterized in that, prescription comprises organic multicomponent phosphinic acid compounds, phosphine carboxylic acid, vinylformic acid copolymer, polymaleic acid and water; Described each weight percentages of components is: organic multicomponent phosphinic acid compounds 1.0～6.0%, and phosphine carboxylic acid 2～12%, vinylformic acid copolymer 10～40%, polymaleic acid 0.2～2%, all the other are water.
2. the described Scale inhibitors of claim 1 is characterized in that, described each weight percentages of components is: organic multicomponent phosphinic acid compounds 1.2～4.8%, and phosphine carboxylic acid 4～10%, vinylformic acid copolymer 16～32%, polymaleic acid 0.4～1.6%, all the other are water.
3. the described Scale inhibitors of claim 1 is characterized in that, described each weight percentages of components is: organic multicomponent phosphinic acid compounds 1.5～4%, and phosphine carboxylic acid 6～8%, vinylformic acid copolymer 16～32%, polymaleic acid 0.6～1.2%, all the other are water.
4. the described Scale inhibitors of claim 1, it is characterized in that: described organic multicomponent phosphinic acid compounds is 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid or ethylene diamine tetra methylene phosphonic acid.
5. the described Scale inhibitors of claim 4, it is characterized in that: described organic multicomponent phosphinic acid compounds is a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid.
6. the described Scale inhibitors of claim 1, it is characterized in that: described phosphine carboxylic acid is a 2-phosphono-1,2,4-butane tricarboxylate or 2-HPAA.
7. the described Scale inhibitors of claim 6, it is characterized in that: described phosphine carboxylic acid is a 2-phosphono-1,2, the 4-butane tricarboxylate.
8. the described Scale inhibitors of claim 1 is characterized in that: described vinylformic acid copolymer is selected from one or more the mixture in vinylformic acid/Propylene glycol monoacrylate, vinylformic acid/methyl acrylate, vinylformic acid/styrene sulfonic acid or the vinylformic acid/itaconic acid copolymer.
9. the described Scale inhibitors of claim 8, it is characterized in that: described vinylformic acid copolymer is vinylformic acid/methyl acrylate copolymer.
10. the preparation method of the described antisludging agent for osmosis-reverse membrane of claim 1, may further comprise the steps: the water, organic multicomponent phosphinic acid compounds, phosphine carboxylic acid, vinylformic acid copolymer and the polymaleic acid that in container, add described ratio successively, stirring and dissolving, acid or alkali with routine are regulated pH value to 1.5～3.5, and the liquid that obtains is Scale inhibitors of the present invention.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100802514A CN101497481B (en) | 2009-03-17 | 2009-03-17 | Scale inhibitor for reverse osmosis membrane and preparation thereof |
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|---|---|---|---|
| CN2009100802514A CN101497481B (en) | 2009-03-17 | 2009-03-17 | Scale inhibitor for reverse osmosis membrane and preparation thereof |
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| CN101497481B true CN101497481B (en) | 2011-01-05 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336477B (en) * | 2010-07-28 | 2013-06-05 | 中国石油化工股份有限公司 | Reverse osmosis membrane scale inhibitor |
| CN102399019A (en) * | 2010-09-09 | 2012-04-04 | 中国石油化工股份有限公司 | Reverse osmosis membrane scale inhibitor and application |
| CN102145943A (en) * | 2010-09-15 | 2011-08-10 | 杭州英普水处理技术有限公司 | Distillation sea water desalinating scale inhibition and dispersion agent and preparation method thereof |
| CN102464409A (en) * | 2010-11-04 | 2012-05-23 | 湖北中碧环保科技有限公司 | Preparation method of multielement composite scale inhibitor |
| CN102558421B (en) * | 2010-12-17 | 2013-10-16 | 中国石油天然气股份有限公司 | Method for preparing biodegradable multifunctional scale inhibitor |
| CN103130346A (en) * | 2013-03-25 | 2013-06-05 | 安徽大地熊新材料股份有限公司 | Antisludging agent for high-hardness high-iron content water quality |
| CN103768957A (en) * | 2014-01-23 | 2014-05-07 | 南通苏通分离工程科技有限公司 | Reverse osmosis membrane scale inhibitor and preparation method thereof |
| CN106110896A (en) * | 2016-06-28 | 2016-11-16 | 安徽松泰包装材料有限公司 | A kind of reverse osmosis membrane antisludging agent |
| CN107261855B (en) * | 2017-07-20 | 2021-03-19 | 首钢集团有限公司 | Reverse osmosis scale inhibitor |
| CN113816504A (en) * | 2021-09-24 | 2021-12-21 | 南京开广化工有限公司 | Coal gasification ash water dispersing agent and preparation method thereof |
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