CN100509653C - Low-phosphorus antiincrustation corrosion inhibitor and use thereof - Google Patents
Low-phosphorus antiincrustation corrosion inhibitor and use thereof Download PDFInfo
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- CN100509653C CN100509653C CNB2004100736651A CN200410073665A CN100509653C CN 100509653 C CN100509653 C CN 100509653C CN B2004100736651 A CNB2004100736651 A CN B2004100736651A CN 200410073665 A CN200410073665 A CN 200410073665A CN 100509653 C CN100509653 C CN 100509653C
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Abstract
This invention relates to a sort of low-phosphor scale-corrosion inhibitor which comprises 2-phospinobutane-1, 2, 4-tricarboylic acid (PBTCA) (or/ and 2-hydroxyphonoacetic acid (HPAA)), zinc salts, molyadate or tungstate and carboxyl-containing copolymer, copper corrosion inhibitor (needed or not conditionally). This low-phosphor scale-corrosion inhibitor can be used to treat recirculated cooling-water in ways such as adjusting pH of high-hardness and high-alkalinity water or treating low-alkalinity and low-hardness water. Its phosphor concentration in recirculated water is no more than 1mg/L, reducing the hazard of phosphor discharge to environment.
Description
Technical field
The present invention relates to a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor and application in recirculated cooling water is handled.
Background technology
The recirculated cooling water processing mainly solves fouling in the circulating water system, corrosion and microorganism and endangers three aspect problems.For reaching this purpose, must filter out the water treatment prescription of a suitable condition of water quality.Water treatment prescription develops into organic entirely, organic zinc salt and molybdenum system prescription by the earliest chromium system, phosphorus system; The circulating water treatment method also by single inhibition corrosive acid process, carries out the transition to the not basic process of adjust pH.Listed the evolution of Japanese treatment of cooling water prescription in the table 1.
The Japanese treatment of cooling water prescription of table 1 development history
The appearance of basic process has made things convenient for on-the-spot operation, but its application is subjected to the restriction of certain condition, is in particular in provincialism restriction (water hardness height difference) and powder performance restriction.The water quality lower (as China's south water system) to hardness, principal contradiction is the etching problem of heat-exchange equipment, moves under alkaline condition, can slow down corrosive and carry out, basic process is a kind of more satisfactory treatment process; But the water quality higher (as northern China underground water) to hardness, what itself will solve is scale problems, and alkaline condition is one of factor that causes fouling, therefore if high hardness water moves under the alkaline condition of adjust pH not, must improve the scale-inhibiting properties of its Scale inhibitors, otherwise be difficult to keep certain cycles of concentration and good scale inhibition performance, but the performance of water treatment agent is difficult to satisfy this condition at present.Therefore will improve the high hardness water cycles of concentration, the way that adopts is an adjust pH at present, and the total phosphorus control in the recirculated water is also higher, is generally 7-10mg/L.
A lot of rivers, lake cause aquatic plants growth out of control because of entering a large amount of phosphorus in the world wide simultaneously, and dissolved oxygen in water exhausts, final water quality deterioration, aquatic animals and plants disappearance.The red tide that China's Coastal Areas took place frequently and on a large scale in recent years is also relevant with nutraceutical discharging such as a large amount of phosphorus, has caused huge disaster to aquatic products breed and natural, ecological.In recent years, Taihu Lake, Dianchi Lake Basin, reservoir area of Three Gorges forced sale and use low-phosphorous articles for washing, after the Shandong Province, Liaoning Province announces to prohibit phosphorus recently comprehensively, in the hope of reducing the phosphorus discharging in natural water.Now, low-phosphorous articles for washing, low-phosphor water treatment agent have become the focus of research.Along with the raising of environmental consciousness, the further strictness of environmental regulation, many countries have begun the discharging of phosphorus restriction, have promoted development low-phosphorous, without phosphorus prescription.
Summary of the invention
The contriver discovers: adopt low-phosphorous medicament 2-phosphonic acid butane-1,2, the 4-tricarboxylic acid (is a 2-phosphonate group-1,2,4-butane tricarboxylate, PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA) and zinc salt, molybdate or tungstate and contain that the carboxylic acid-based copolymer is composite to have good inhibition and a scale-inhibiting properties, can save the consumption that uses the high organic phosphine medicament of other phosphorus content or reduce PBTCA and/or HPAA, be applied to circulating water treatment and can reduce organic phosphine medicament commonly used because of the high harm of phosphorus content to environment.
The object of the present invention is to provide a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor, it has good resistance CaCO
3The dirt function also has Zn in the satisfactory stability water
2+Ability and corrosion inhibition, simultaneously can reduce the harm of phosphorus to environment, satisfy the environmental requirement of increasingly stringent.
Another object of the present invention is that composite scale-inhibiting corrosion inhibitor of the present invention is applied to recirculated cooling water to be handled.
For achieving the above object, the invention provides a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor, it is by 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), zinc salt, molybdate or tungstate and contain that the carboxylic acid-based copolymer forms, effective concentration with respect to pending each component of aqueous solution total amount is: 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA) are 1-3mg/L, Sodium orthomolybdate or sodium wolframate are 2-15mg/L, and zinc salt concentration is (with Zn
2+Meter) be 1.5-5mg/L, containing carboxylic acid-based copolymer's concentration is 2-20mg/L.
The effect of each medicament is in the low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention: 2-phosphonic acid butane-1,2, and 4-tricarboxylic acid (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), contain the carboxylic acid-based copolymer and play scale inhibition and dissemination, stop CaCO
3The deposition of dirt and suspended substance, zinc salt, 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), molybdate or tungstate play corrosion inhibition, wherein contain the carboxylic acid-based copolymer and also play zinc salt in the stable circulation water, zinc salt can be stabilized in the water well, the performance corrosion inhibition.
Molybdate of the present invention is a Sodium orthomolybdate; Tungstate is a sodium wolframate.
Of the present inventionly contain the carboxylic acid-based copolymer for copolymer or terpolymer, be preferably at least a vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer (T225) that is selected from, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid (AMPS) multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropane phosphonic acids/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said acrylate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
Zinc salt of the present invention is selected from zinc sulfate or zinc chloride.
When in the circulation cooling water system, using copper material equipment, composite scale-inhibiting corrosion inhibitor of the present invention also can contain heterogeneous ring compound as copper material corrosion inhibitor, described copper material corrosion inhibitor is preferably from mercaptobenzothiazole and benzotriazole, and the effective concentration of copper material corrosion inhibitor is 0.5-1.5mg/L.
Anti-incrustation corrosion inhibitor of the present invention, because of PBTCA wherein, the HPAA phosphorus content is low and consumption less make anti-incrustation corrosion inhibitor in recirculated water total phosphorus (with PO
4 3-Meter) content is smaller or equal to 1mg/L.
Available ordinary method prepares composite scale-inhibiting corrosion inhibitor of the present invention, the reinforced order of each component is unimportant, for example can be with PBTCA and/or HPAA, Sodium orthomolybdate or sodium wolframate, zinc salt, contain carboxylic acid-based copolymer and copper material corrosion inhibitor (if any) and water by predetermined mixed, can make required low-phosphorous composite scale-inhibiting corrosion inhibitor.
Composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3The dirt function also has Zn in the good stabilize water
2+Ability and corrosion inhibition.Can reduce simultaneously the content of total phosphorus in the recirculated cooling water, reduce organic phosphine medicament commonly used, satisfy the environmental requirement of increasingly stringent because of the high harm of phosphorus content to environment.
Composite scale-inhibiting corrosion inhibitor of the present invention is particularly suitable for the recirculated cooling water of highly corrosive water quality and handles, as calcium hardness and, total alkalinity sum is high hard, the high-alkali water quality handled of the above adjust pH of 300mg/L and calcium hardness and the total alkalinity sum is following low firmly, the recirculated cooling water processing of hanging down buck matter of 100mg/L.
When to handle calcium hardness and total alkalinity sum be high hard, high-alkali water quality more than the 300mg/L, generally employing added sour adjust pH technology.Add earlier low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention, and to add acid control pH value be 6.5～8.5, be preferably 7.8～8.3, described acid is sulfuric acid, nitric acid etc., and its add-on is so that the pH value is adjusted to 6.5～8.5, is preferably 7.8～8.3 to be as the criterion.
Handle calcium hardness and total alkalinity sum be below the 100mg/L low hard, hang down buck matter, directly add low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention, need not control the pH value.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
The test raw water quality sees Table 2.
The former water of table 2 test
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | PH | Specific conductivity | Total molten solid |
| High hard, high-alkali water quality | 265 | 380 | 370 | 78 | 120 | 7.8 | 1020 | 756 |
| Low hard, low buck matter | 25 | 31 | 37 | 9 | 11 | 7.4 | 120 | 69 |
Annotate: 1) pH does not have unit, and specific conductivity is μ s/cm, and its counit is mg/L, Ca
2+, total alkalinity, total hardness be all with CaCO
3Meter, down together.
2), Ca
2+Represent calcium hardness, down together.
" water coolant analysis and the test method " that the measuring method of water quality is write with reference to production department of China PetroChemical Corporation and development division (1993, general petrochemical works, Anqing information center publishes).
The assessment of performance method of following embodiment gained composite scale-inhibiting corrosion inhibitor is as follows:
Resistance calcium carbonate scale performance is got the former water of test, adding is by the drug concentration that embodiment added, evaporation concentration in 80 ± 1 ℃ of waters bath with thermostatic control, and (low hard, low buck matter is to 5 times of cycles of concentration to cycles of concentration, high hard, high-alkali water quality is to 2 times of cycles of concentration), remain Ca in the sampling analysis water
2+Concentration, make blank sample simultaneously, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C0)/(nC1-C0) * 100%
C: actual measurement Ca
2+Concentration (mg/L)
C0: the Ca of blank sample
2+Concentration (mg/L)
C1: the Ca in the former water
2+Concentration (mg/L)
N: be cycles of concentration
Stablize the zinc salt performance and get distilled water preparation Ca
2+Concentration is 250mg/L, and basicity is 250mg/L and Zn
2+Be the test water of 5mg/L, add medicament, in 80 ± 1 ℃ of waters bath with thermostatic control, left standstill 10 hours, remain Zn in the sampling analysis water by the drug concentration that embodiment added
2+Concentration, make blank sample simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C0)/(C1-C0) * 100%
C: actual measurement Zn
2+Concentration (mg/L)
C0: the Zn of blank sample
2+Concentration (mg/L)
C1: the Zn in the former water
2+Concentration (mg/L)
Resistance zinc rate is high more, and the stability of zinc salt in water is good more, and it is good more to illustrate that medicament is stablized the performance of zinc salt.
Corrosion inhibition is fixed on the test piece of 20# qualitative carbon steel on the lacing film instrument, and (low hard, low buck matter is to 5 times of cycles of concentration, not adjust pH to put into the test water that is added with the drug concentration that adds by embodiment; High hard, high-alkali water quality is to 2 times of cycles of concentration, and use the sulfuric acid adjust pH) in, 40 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72 hours, the weight of test piece before and after the record test, calculating average corrosion rate.
The average corrosion rate calculation formula is: F=(C * △ W)/(A * T * ρ)
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10
7
△ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
Embodiment 1
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 4.0g effective content and be 50% PBTCA, Sodium orthomolybdate 8.0g, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 26.7g, be dissolved in the 50.4g water, add the 10.9g Zinc vitriol at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low buck, adding respectively by the drug concentration of 100mg/L with the medicament for preparing, PBTCA, Sodium orthomolybdate, T225, Zn in the water
2+Effective concentration be respectively 2mg/L, 8mg/L, 8mg/L, 2.5mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.7mg/L.
Embodiment 2
Taking by weighing the 5.0g effective content and be 40% HPAA, sodium wolframate 5.0g, solid content and be 30% AA/AMPS/HPA contains carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number is 0.078dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=70/15/15) 20.0g, be dissolved in the 65.8g water, add the 4.2g zinc chloride at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When adding in height hard, high-alkali (with sulfuric acid adjust pH 8.0-8.4) and low hard, low alkali test water respectively by the drug concentration of 100mg/L with the liquid medicine for preparing, HPAA, sodium wolframate, AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer, Zn simultaneously in the water
2+Effective concentration be respectively 2mg/L, 5mg/L, 6mg/L, 2mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.9mg/L.
Embodiment 3
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 2.5g effective content and be 40% HPAA, 3.0g effective content and be 50% PBTCA, Sodium orthomolybdate 8.0g, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 26.7g, be dissolved in the 48.9g water, add the 10.9g Zinc vitriol at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low alkali test water, adding respectively by the drug concentration of 100mg/L with the liquid medicine for preparing, HPAA, PBTCA, Sodium orthomolybdate, T225, Zn in the water
2+Effective concentration be respectively 1mg/L, 1.5mg/L, 8mg/L, 8mg/L, 2.5mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 1.0mg/L.
Embodiment 4
Taking by weighing the 5.0g effective content and be 40% HPAA, sodium wolframate 7.0g, solid content and be 30% AA/AMPS contains carboxylic acid group and sulfonic group copolymer simultaneously (limit viscosity number is 0.075dl/g 30 ℃ the time, weight ratio is AA/AMPS=70/30) 30.0g, be dissolved in the 49.2g water, add the 8.8g Zinc vitriol at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When adding in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low alkali test water respectively by the drug concentration of 100mg/L with the liquid medicine for preparing, HPAA, sodium wolframate, AA/AMPS contain carboxylic acid group and sulfonic group copolymer, Zn simultaneously in the water
2+Effective concentration be respectively 2mg/L, 7mg/L, 9mg/L, 2mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 6.1mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.9mg/L.
Embodiment 5
Taking by weighing the 5.0g effective content and be 50% PBTCA, Sodium orthomolybdate 10.0g, solid content is 30% T225 (limit viscosity number is 0.072dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 16.7g and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number be 0.075dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=60/20/20) 20.0g, be dissolved in the 42.0g water, add the 6.3g zinc chloride at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When adding in height hard, high-alkali (with sulfuric acid adjust pH 7.6-8.0) and low hard, low alkali test water respectively by the drug concentration of 100mg/L with the liquid medicine for preparing, PBTCA, Sodium orthomolybdate, T225, AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer, Zn simultaneously in the water
2+Effective concentration be respectively 2.5mg/L, 10mg/L, 5mg/L, 6mg/L, 3mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.9mg/L.
Embodiment 6
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 4.0g effective content and be 50% PBTCA, Sodium orthomolybdate 15.0g, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 20.0g, be dissolved in the 50.1g water, add the 10.9g Zinc vitriol at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low buck, adding respectively by the drug concentration of 100mg/L with the medicament for preparing, PBTCA, Sodium orthomolybdate, T225, Zn in the water
2+Effective concentration be respectively 2mg/L, 15mg/L, 6mg/L, 2.5mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.7mg/L.
Embodiment 7
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 4.0g effective content and be 50% PBTCA, Sodium orthomolybdate 3.0g, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 60.0g, be dissolved in the 24.8g water, add the 8.2g zinc chloride at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low buck, adding respectively by the drug concentration of 100mg/L with the medicament for preparing, PBTCA, Sodium orthomolybdate, T225, Zn in the water
2+Effective concentration be respectively 2mg/L, 3mg/L, 18mg/L, 4mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.7mg/L.
Comparative Examples 1
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 40.0g solid content and be the terpolymer of 30% AA/AMPS/HPA, weight ratio is AA/AMPS/HPA=60/20/20), active ingredient is 50% PBTCA 9.0g, HEDP 9.0g and 6.3g Zinc Chloride Anhydrous, add in the 35.7g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in height hard, high-alkali (with sulfuric acid adjust pH 7.6-8.0) and low hard, low alkali test water by the drug concentration of 100mg/L with the liquid medicine for preparing, the terpolymer of AA/AMPS/HPA, PBTCA, HEDP, Zn
2+Effective concentration be respectively 12mg/L, 4.5mg/L, 4.5mg/L, 3mg/L, total phosphorus is (with PO in the water
4 3-meter) be 6.1mg/L.
Comparative Examples 2
Taking by weighing the 2.0g effective content and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Sodium orthomolybdate 10.0g, solid content is 30% T225 (limit viscosity number is 0.072dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 16.7g and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number be 0.075dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=60/20/20) 20.0g, be dissolved in the 45.0g water, add the 6.3g zinc chloride at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When adding in height hard, high-alkali (with sulfuric acid adjust pH 7.6-8.0) and low hard, low alkali test water respectively by the drug concentration of 100mg/L with the liquid medicine for preparing, HEDP, Sodium orthomolybdate, T225, AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer, Zn simultaneously in the water
2+Effective concentration be respectively 1mg/L, 10mg/L, 5mg/L, 6mg/L, 3mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 1.0mg/L.
Comparative Examples 3
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 4.0g effective content and be 50% PBTCA, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 26.7g, be dissolved in the 58.4g water, add the 10.9g Zinc vitriol at last, it is fully dissolved, shake up, promptly obtain the 100.0g medicament of required preparation.
When in height hard, high-alkali (with sulfuric acid adjust pH 7.8-8.2) and low hard, low buck, adding respectively by the drug concentration of 100mg/L with the medicament for preparing, PBTCA, T225, Zn in the water
2+Effective concentration be respectively 2mg/L, 8mg/L, 2.5mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.7mg/L.
Carry out static-state scale inhibition test and rotary hanging plate corrosion test by the above-mentioned concentration that adds, resistance calcium carbonate scale rate, resistance zinc rate and corrosion speed see Table 3,4.
The scale inhibitor effect of corrosion inhibiting and descaling agent in high hard, the high-alkali water quality of table 3
| Embodiment | Lime carbonate scale inhibition performance (%) | Resistance zinc rate (%) | Corrosion speed (mm/a) |
| 1 | 80.6 | 58.9 | 0.020 |
| 2 | 80.1 | 54.7 | 0.015 |
| 3 | 79.3 | 58.3 | 0.017 |
| 4 | 89.7 | 60.5 | 0.014 |
| 5 | 79.1 | 63.9 | 0.013 |
| 6 | 78.9 | 50.3 | 0.011 |
| 7 | 81.3 | 69.5 | 0.012 |
| Comparative Examples 1 | 81.7 | 50.7 | 0.023 |
| Comparative Examples 2 | 75.5 | 45.9 | 0.051 |
| Comparative Examples 3 | 80.6 | 58.9 | 0.115 - |
The scale inhibitor effect of corrosion inhibiting and descaling agent in low hard, the low buck matter of table 4
| Embodiment | Lime carbonate scale inhibition performance (%) | Resistance zinc rate (%) | Corrosion speed (mm/a) |
| 1 | 99.4 | 58.9 | 0.034 |
| 2 | 99.1 | 54.7 | 0.029 |
| 3 | 97.8 | 58.3 | 0.032 |
| 4 | 98.4 | 60.5 | 0.025 |
| 5 | 97.9 | 63.9 | 0.020 |
| 6 | 97.2 | 50.3 | 0.019 |
| 7 | 99.6 | 69.5 | 0.023 |
| Comparative Examples 1 | 97.8 | 50.7 | 0.037 |
| Comparative Examples 2 | 95.4 | 45.9 | 0.075 |
| Comparative Examples 3 | 99.4 | 58.9 | 0.121 |
Table 3 data declaration, composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3Function also has Zn in the satisfactory stability water
2+Ability and corrosion inhibition, can reduce simultaneously the content of total phosphorus in the recirculated cooling water.
Embodiment 8
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), and controlled variable is as follows.
Water quality: high hard, high-alkali water quality in the table 2
Cycles of concentration: A tower 4.0 ± 0.2 B towers 4.0 ± 0.2
PH:A tower control 8.0 ± 0.2 B towers control 8.0 ± 0.2
Flow velocity: 1.0m/s
Medicament: the compound of A tower: embodiment 1
B tower: the compound of Comparative Examples 1
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality sees Table 2.
The dynamic analog test test tube the results are shown in Table 5.
Table 5 dynamic analog test test tube result
Stipulate that the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a among standard GB 50050-95 " Code for design of industrial recirculating cooling water treatment " 3.1.6; " the small-sized experimental analogic method of testing laboratory " regulation corrosion of Carbon Steel speed is " fine " level between 0-0.028mm/a in " the water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, be " good " level between 0.028-0.056mm/a, be " can allow " level at 0.056-0.070mm/a; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.
This shows, use low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention and at hard, the high-alkali water quality cycles of concentration of height be under 4 the situation, the erosion rate of test tube is 0.023mm/a, reaches China Petrochemical Industry's " fine level " standard, adhere to speed 5.4mcm, reach " fine level " standard; Be better than Comparative Examples and be 4 situation at hard, the high-alkali water quality cycles of concentration of height.
Claims (10)
1. low-phosphorous composite scale-inhibiting corrosion inhibitor, it is by 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, zinc salt, molybdate or tungstate and contain that the carboxylic acid-based copolymer forms, effective concentration with respect to pending each component of aqueous solution total amount is: 2-phosphonic acid butane-1,2, and 4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid are 1-3mg/L, Sodium orthomolybdate or sodium wolframate are 2-15mg/L, and zinc salt concentration is with Zn
2+Count 1.5-5mg/L, containing carboxylic acid-based copolymer's concentration is 2-20mg/L.
2. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that described molybdate is a Sodium orthomolybdate; Tungstate is a sodium wolframate.
3. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that containing the carboxylic acid-based copolymer and is copolymer or terpolymer.
4. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that containing the carboxylic acid-based copolymer and is at least a vinylformic acid/Propylene glycol monoacrylate multipolymer that is selected from, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropane phosphonic acids/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.
5. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that described zinc salt is selected from zinc sulfate or zinc chloride.
6. according to each described anti-incrustation corrosion inhibitor of claim 1-5, it is characterized in that described anti-incrustation corrosion inhibitor also contains heterogeneous ring compound as copper material corrosion inhibitor.
7. anti-incrustation corrosion inhibitor according to claim 6 is characterized in that described copper material corrosion inhibitor selected from mercapto benzothiazole and benzotriazole.
8. according to claim 6 or 7 described anti-incrustation corrosion inhibitors, it is characterized in that the effective concentration with respect to pending aqueous solution total amount copper material corrosion inhibitor is 0.5-1.5mg/L.
9. the purposes of each described anti-incrustation corrosion inhibitor of claim 1-8 is characterized in that described composite scale-inhibiting corrosion inhibitor is applicable to the recirculated cooling water processing to highly corrosive water quality.
10. purposes according to claim 9 is characterized in that highly corrosive water quality is that the hard and total alkali sum of calcium is 300mgL
-1More than and high hard, the high-alkali water quality handled of adjust pH or calcium firmly and the total alkali sum be 100mgL
-1Below low firmly, as to hang down alkali water quality.
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| CN106315880A (en) * | 2016-09-28 | 2017-01-11 | 沈阳建筑大学 | Scaling corrosion inhibitor and preparation method thereof |
| CN106517545A (en) * | 2016-07-31 | 2017-03-22 | 乌鲁木齐德安东升环保设备有限公司 | Efficient low-phosphorus macromolecule scale inhibition corrosion inhibitor and preparation method thereof |
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