CN1202028C - Pretreatment filming agent and pretreatment filming method for circulating cooling water system - Google Patents
Pretreatment filming agent and pretreatment filming method for circulating cooling water system Download PDFInfo
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- CN1202028C CN1202028C CNB021585806A CN02158580A CN1202028C CN 1202028 C CN1202028 C CN 1202028C CN B021585806 A CNB021585806 A CN B021585806A CN 02158580 A CN02158580 A CN 02158580A CN 1202028 C CN1202028 C CN 1202028C
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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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Abstract
The present invention relates to a pre-filming agent suitable for a circulating cooling water system and a pre-filming method thereof. The pre-filming agent is prepared from following components, in weight percentage: 2% to10% of phosphoric acid, 1% to 10% of zinc dihydrogen phosphate, 4.5% to 10.5% of copolymer containing carboxylic acid, 5% to 18% of organic phosphonic acid, 0.5% to 2.0% of azimidobenzene and balancing amount of water. The pre-filming agent can pre-film equipment and pipelines before being used in normal operation for a circulating cooling water system, and the addition level is 200 to 600 mg of pre-filming agent /L of water. The pre-filming agent has the advantages that when surface water or underground water is used as supplementary water in a circulating cooling water system under a natural operation condition (high alkalinity), the pre-filming agent can be used for pre-filming equipment and pipelines in a circulating cooling water system, the pH value of water can reach as high as 8.4, the use range of the pre-filming agent is enlarged, and simultaneously, the pre-filming agent does not need souring or special souring equipment, saves costs and simplifies operation.
Description
Technical field
The present invention relates to a kind of prefilming agent of recirculating cooling water system and prefilming method of recirculating cooling water system of being suitable for, relate in particular to a kind of prefilming method of sour circulating water system driving that be used for not adding with prefilming agent and recirculating cooling water system.
Background technology
The whole organic basic water technology is the method that present circulating water treatment is usually adopted, and this technology has need not add acid, advantage that erosion rate is low.Therefore because the scene does not add sour equipment, require pre-film to carry out not adding under the sour condition.Before 1998, adopt the solid prefilming agent of S204 to add the method for multipolymer, promptly Sodium hexametaphosphate 99 adds zinc salt and adds the method that multipolymer adds amino sulfonic acid more, the problem that runs into during pre-film is that medicament is added in the system, a lot of insolubless are arranged, the turbidity height (greater than 20mg/L) of water, pre-film effect is undesirable.If can adopt the novel prefilming method do not add sulfuric acid and can increase pre-film effect to prefilming agent is an effective way that solves enterprise's recirculated water safety operation.
Chinese patent application CN1193609A discloses clean-out system, prefilming agent and cleaning thereof, the prefilming method that is used for dirts such as cleaning system rust deposite, incrustation scale, foundry loam in a kind of circulating water system, it cleans prefilming agent and is made of biological enzyme scavenging agent, biostats, inorganic salt complex agent and conventional water quality stabilizer monomer, characteristics are that inorganic salt complex agent is made up of silicate, manganate, carbonate, preferably add ortho-phosphoric acid or orthophosphoric acid salt in the inorganic salt complex agent again.Cleaning prefilming method is under the normal operating condition of circulating water regiment commander thermal load, biological enzyme scavenging agent, biostats, inorganic salt complex agent and conventional water quality stabilizer are joined in the recirculated water by the specific concentrations of always possessing the water yield respectively, and kept this concentration 15-60 days, the anti-incrustation corrosion inhibitor of this technology is that inorganic salt complex agent is made up of silicate, manganate, carbonate, orthophosphoric acid salt, and is different with the prefilming agent that is used for circulating water system of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of prefilming agent that is suitable for recirculating cooling water system.Use prefilming agent of the present invention that the equipment of circulating water system is carried out pre-film, need not transfer the pH of recirculated water.
Another object of the present invention is to provide a kind of prefilming method of recirculating cooling water system.
For achieving the above object, the invention provides a kind of prefilming agent, described prefilming agent by phosphoric acid, primary zinc phosphate, contain carboxylic acid-based copolymer, organic phospho acid, benzotriazole and water and form, their proportioning is by weight percentage:
Phosphoric acid 2-10%
Primary zinc phosphate 1-10%
Organic phospho acid 5-18%
Benzotriazole 0.5-2.0%
Contain carboxylic acid-based copolymer 4.5-10.5%
Water surplus.
Organic phospho acid of the present invention is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), the 2-phosphonate group-1 of being selected from, 2,4-butane tricarboxylate (PBTCA), hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids.
The carboxylic acid group's of containing of the present invention multipolymer is toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid (AA)/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, vinylformic acid/vinyl 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-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer or acrylic acid/esters multipolymer.Wherein said acrylate is preferably from methyl acrylate (MA), ethyl propenoate, Propylene glycol monoacrylate (HPA).
The present invention also provides a kind of prefilming method of recirculating cooling water system, be characterized in before the equipment and pipeline normal operation input of recirculating cooling water system, add prefilming agent of the present invention in recirculated cooling water, add-on is 200-600mg prefilming agent/L water.
Initial pre-film when making the recirculating cooling water system make up water with surface water or underground water gets final product by handling with prefilming agent of the present invention.
Recirculated cooling water of the present invention is from surface water or underground water, and its calcium ion concn is 80-300mg/L (in lime carbonate, down together), turbidity＜10mg/L.
The using method of prefilming agent is relevant with the calcium ion concn of recirculated cooling water, if the recirculated cooling water calcium ion concn is during greater than 150mg/L, when the aqueous solution that the solution that directly will contain prefilming agent all components of the present invention is phosphoric acid, primary zinc phosphate, contain carboxylic acid-based copolymer, organic phospho acid and benzotriazole adds in the recirculated cooling water, the part has calcium phosphate and separates out, and is unfavorable for film forming.Therefore, when in recirculated cooling water, adding prefilming agent of the present invention, dosing method is slightly different according to the different calcium ionic concn: of the present invention when recirculated cooling water calcium ion concn during greater than 150mg/L, can be earlier will contain benzotriazole and organic phosphine aqueous acid-abbreviation A liquid and add in the recirculated cooling water, and in recirculated cooling water, add phosphoric acid, primary zinc phosphate again and contain the aqueous solution-abbreviation B liquid of carboxylic acid-based copolymer.When described recirculated cooling water calcium ion concn during less than 150mg/L, A liquid B liquid can be mixed in the back adding recirculated water and use, the aqueous solution that also can directly to prepare the solution that contains prefilming agent all components of the present invention be phosphoric acid, primary zinc phosphate, contain carboxylic acid-based copolymer, organic phospho acid and benzotriazole again will this solution adds in recirculated water and uses.When successively or when adding in the recirculated water simultaneously, A liquid and B liquid add by equal proportion with A liquid, B liquid form.
The temperature of recirculated cooling water has certain influence to pre-film speed, and prefilming agent of the present invention helps film forming under the high situation of recirculated cooling water temperature, also can carry out at normal temperatures when the raising temperature of cooling water is had any problem, but will prolong preliminary filming time.Equal film forming smoothly when the temperature of general water coolant is a room temperature to 50 ℃ is a time length difference.When the temperature of water coolant was a room temperature to 50 ℃, the preliminary filming time of prefilming agent of the present invention was 5-48 hour.
Prefilming agent of the present invention can prepare with ordinary method, the reinforced order of each component is unimportant, for example can be with phosphoric acid, primary zinc phosphate, contain carboxylic acid-based copolymer, organic phospho acid, benzotriazole and water by predetermined mixed, can make required prefilming agent.Also can prefilming agent of the present invention be mixed with two kinds of solution, but the reinforced order of component is unimportant in every kind of solution: as benzotriazole, organic phospho acid and water being made into a kind of liquid medicine-A liquid by predetermined mixed according to the needs that use prefilming agent; Again phosphoric acid, primary zinc phosphate, the multipolymer that contains the carboxylic acid group and water are made into another kind of liquid medicine-B liquid by predetermined mixed, so just make required prefilming agent, when the equipment to recirculating cooling water system carries out pre-film, can earlier A liquid be added in the recirculating cooling water system, again to wherein adding B liquid.B liquid of the present invention can also following manner be prepared:
The first phosphoric acid dihydro zinc aqueous solution of preparation phosphoric acid or non-phosphoric acid: with phosphoric acid and zinc oxide with 2.1: 1-12: 1 mixed in molar ratio, phosphoric acid and zinc oxide are reacted the generation primary zinc phosphate in mixing process:
Usually poly-phosphate or phosphoric acid salt add the pre-film scheme of zinc salt, need to adopt the method that pH value is turned down and need the strict pH of control value, as the pH value that need add sour controlled chilling water when using poly-phosphate/zinc salt/multipolymer prefilming agent to carry out pre-film is 5.5-6.5.And the advantage of prefilming agent of the present invention is: when making the make up water of recirculating cooling water system with surface water or underground water under natural operational conditions, can carry out pre-film to the equipment and the pipeline of recirculating cooling water system with prefilming agent of the present invention, the pH value of water quality can be up to 8.4, simultaneously do not need to add acid and special use and add sour equipment, save expense, simplified operation.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
" rotary hanging plate weight-loss method " in " water coolant analysis and the test method " that the following examples are all write according to production department of China PetroChemical Corporation and development division (1993, general petrochemical works, Anqing information center publishes) carries out pre-film rotary hanging plate corrosion test.Test temperature is 30-50 ℃ in " rotary hanging plate weight-loss method ", and the test piece rotating speed is 75 rev/mins (rpm), and test period is 5-40 hour, and the lacing film material is a carbon steel.The test water of following embodiment is from the surface water of Beijing area or underground water.Test water water quality is: Ca
2+(with CaCO
3Meter, down together) 80-300mg/L, total alkalinity is (with CaCO
3Meter, down together) 80-280mg/L, Cl
-13-142mg/L, SO
4 2-16-139mg/L, pH7.4-8.4, turbidity 1.2-4.2mg/L." water coolant analysis and test method) " that the mensuration of water-quality guideline is write according to production department of China PetroChemical Corporation and development division carries out.
After pre-film finishes, take out test piece, at first observe and have or not dirt settling in the test piece,, need wash away dirt settling with tap water if dirt settling is arranged.Use the dehydrated alcohol wiping, dry up with hair dryer.Observe homogeneity, the consistency of colour of rete afterwards.Use CuSO
4The pre-film effect of-NaCl solution method check carbon steel lacing film.With the CuSO for preparing
4In the test piece that-NaCl drips of solution is crossed in pre-film and not pre-film, measure the red required time of point of appearance in two test pieces with stopwatch simultaneously, the time difference of the two is big more, and the expression pre-film effect is good more.The red required time of point is appearred in the test piece of all pre-films compare, can distinguish the quality of every kind of pre-film medicament pre-film effect.
CuSO
4The compound method of-NaCl solution: take by weighing 15g sodium-chlor and 5g copper sulfate and be dissolved in the 100mL distilled water and get final product.
Embodiment 1
Process for preparation: preparation A liquid, each 50g of B liquid
0.92g zinc oxide is mixed with 10g phosphoric acid, stirring and dissolving, and adding 8g water, adding the 31.08g solid content then and be 30% AA/AMPS/HPA contains the sulfonic group terpolymer (HPA is a hydroxypropyl acrylate, weight ratio is AA/AMPS/HPA=60/20/20), stir, shake up, promptly obtain the 50gB liquid of required preparation; It is that 50% HPAA and 14.5g active ingredient are among 50% the HEDP that the 0.8g benzotriazole is dissolved in the 4.5g active ingredient, adds 30.2g water then, shakes up, and promptly obtains the 50gA liquid of required preparation.
The concentration of the above-mentioned medicament A liquid for preparing by 250mg/L is added in test water, add B liquid 250mg/L then, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+155mg/L, total alkalinity 160mg/L, Cl
-41mg/L, SO
4 2-18mg/L, pH7.6, turbidity 1.2mg/L.Test temperature is 30 ℃, and test period is 24 hours, and test-results sees Table 1.
Dosage 500mg/L (A liquid 250mg/L and B liquid 250mg/L sum) with a kind of prefilming agent during by test is a basic calculation, by weight percentage, and wherein:
Phosphoric acid 7.8%
Primary zinc phosphate 2.9%
Organic phospho acid 9.5%
Benzotriazole 0.8%
Contain carboxylic acid-based copolymer 9.3%
Water 69.7%
Embodiment 2
Process for preparation: preparation A liquid, each 50g of B liquid
1.72g zinc oxide is mixed with 7g phosphoric acid, and stirring and dissolving adds the 30g solid content and is 30% AA/AMPS and contains sulfonic group copolymer (weight ratio is AA/AMPS=60/40), adds water 11.2g, and fully dissolving shakes up, and promptly obtains the B liquid of required preparation.With the 24g active ingredient be 50% HEDP join active ingredient be 40% among the two phosphorus sulfonic acid 10g, add the 1.3g benzotriazole again, stirring and dissolving adds entry 14.7g then, fully dissolving shakes up, and promptly obtains the A liquid of required preparation.
The drug concentration of the above-mentioned liquid medicine A liquid for preparing by 150mg/L added in test water, add B liquid 150mg/L then in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+231mg/L, total alkalinity 243mg/L, Cl
-79mg/L, SO
4 2-135mg/L, pH8.1, turbidity 1.6mg/L.Test temperature is 40 ℃, and test period is 14 hours, and test-results sees Table 1.
Dosage 300mg/L (A liquid 150mg/L and B liquid 150mg/L sum) with a kind of prefilming agent during by test is a basic calculation, by weight percentage, and wherein:
Phosphoric acid 2.8%
Primary zinc phosphate 5.5%
Organic phospho acid 16.0%
Benzotriazole 1.3%
Contain carboxylic acid-based copolymer 9.0%
Water 65.4%
Embodiment 3
Process for preparation: preparation A liquid, each 50g of B liquid.
1.2g zinc oxide is mixed with 9g phosphoric acid, and stirring and dissolving adds the 20g solid content and is 30% AA/AMPS and contains sulfonic group copolymer (weight ratio is AA/AMPS=70/30), adds water 19.8g, promptly obtains the 50gB liquid of required preparation; With 1g benzotriazole, active ingredient is that 30% 8gEDTMP and 26g HEDP mix, and stirring and dissolving adds entry 15g then, and fully dissolving shakes up, and promptly obtains the 50gA liquid of required preparation.
The drug concentration of the above-mentioned liquid medicine A liquid for preparing by 200mg/L added in test water, add B liquid 200mg/L then in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+155mg/L, total alkalinity 123mg/L, Cl
-106mg/L, SO
4 2-34mg/L, pH8.4, turbidity 1.6mg/L.Test temperature is 25 ℃, and test period is 40 hours, and test-results sees Table 1.
Dosage 400mg/L (A liquid 200mg/L and B liquid 200mg/L sum) with a kind of prefilming agent during by test is a basic calculation, by weight percentage, and wherein:
Phosphoric acid 6.1%
Primary zinc phosphate 3.8%
Organic phospho acid 15.4%
Benzotriazole 1.0%
Contain carboxylic acid-based copolymer 6.0%
Water 67.7%
Embodiment 4
Process for preparation: preparation A liquid, each 50g of B liquid.
2.5g phosphoric acid and 9g primary zinc phosphate are mixed, stirring and dissolving, adding 35g solid content is 30% AA/MA/HPA multipolymer (weight ratio is AA/MA/HPA=70/15/15), adds water 3.5g, promptly obtains the 50gB liquid of required preparation; With 1.3g benzotriazole, active ingredient is that 50% 16gPBTCA and active ingredient are that 50% 19g ATMP mixes, and stirring and dissolving adds entry 13.7g then, and fully dissolving shakes up, and promptly obtains the 50gA liquid of required preparation.
The drug concentration of the above-mentioned liquid medicine A liquid for preparing by 150mg/L added in test water, add B liquid 150mg/L then in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+231mg/L, total alkalinity 243mg/L, Cl
-79mg/L, SO
4 2-135mg/L, pH8.1, turbidity 1.6mg/L.Test temperature is 30 ℃, and test period is 35 hours, and test-results sees Table 1.
Dosage 300mg/L (A liquid 150mg/L and B liquid 150mg/L sum) with a kind of prefilming agent during by test is a basic calculation, by weight percentage, and wherein:
Phosphoric acid 2.5%
Primary zinc phosphate 9.0%
Organic phospho acid 17.5%
Benzotriazole 1.3%
Contain carboxylic acid-based copolymer 10.5%
Water 59.2%
Embodiment 5
Process for preparation: preparation 100g prefilming agent
0.9g zinc oxide is mixed with 8g phosphoric acid, stirring and dissolving, adding the 20g solid content then respectively and be 30% AA/AMPS, to contain sulfonic group copolymer (weight ratio is AA/AMPS=55/45), 1g benzotriazole, active ingredient be 50% 22gHEDP, add at last in the 48.1g water, stir fully dissolving, promptly obtain the 100g prefilming agent of required preparation.By weight percentage, wherein:
Phosphoric acid 5.8%
Primary zinc phosphate 2.9%
Organic phospho acid 11.0%
Benzotriazole 1.0%
Contain carboxylic acid-based copolymer 6.0%
Water 73.3%
The drug concentration of the above-mentioned prefilming agent for preparing by 500mg/L added in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality: Ca
2+135mg/L, total alkalinity 123mg/L, Cl
-46mg/L, SO
4 2-24mg/L, pH8.4, turbidity 3.6mg/L.Test temperature is 30 ℃, and test period is 24 hours, and test-results sees Table 1.
Embodiment 6
Process for preparation: preparation 100g prefilming agent
1.72g zinc oxide is mixed with 9g phosphoric acid, stirring and dissolving, adding the 25g solid content then respectively and be 30% AA/AMPS/HPA, to contain sulfonic group terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), 8g active ingredient be that 50% HEDP, 16g active ingredient are 50% thionamic acid two methene phosphonic acids, the 10g active ingredient be 40% to two phosphono and sulfonics, 1g benzotriazole, reach stirring and dissolving in the 29.28g water, promptly obtain the 100g liquid medicine of required preparation.By weight percentage, wherein:
Phosphatase 24 .8%
Primary zinc phosphate 5.5%
Organic phospho acid 16.0%
Benzotriazole 1.0%
Contain carboxylic acid-based copolymer 7.5%
Water 65.2%
The drug concentration of the above-mentioned prefilming agent for preparing by 400mg/L added in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality Ca
2+85mg/L, total alkalinity 113mg/L, Cl
-26mg/L, SO
4 2-34mg/L, pH8.0, turbidity 4.2mg/L.Test temperature is 50 ℃, and test period is 6 hours, and test-results sees Table 1.
Embodiment 7
Process for preparation: preparation 100g prefilming agent
1.72g zinc oxide is mixed with 9g phosphoric acid, stirring and dissolving, adding the 30g solid content then respectively and be 30% AA/AMPS/HPA, to contain sulfonic group terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), 1.9g benzotriazole, 8g active ingredient be that 50% HPAA, 8g active ingredient are that 50% HEDP and 20g active ingredient are 50% taurine two methene phosphonic acids, be dissolved in the 21.38g water, stir fully dissolving, shake up, promptly obtain the 100g liquid medicine of required preparation.By weight percentage, wherein:
Phosphatase 24 .8%
Primary zinc phosphate 5.5%
Organic phospho acid 18.0%
Benzotriazole 1.9%
Contain carboxylic acid-based copolymer 9.0%
Water 60.8%
The drug concentration of the above-mentioned prefilming agent for preparing by 300mg/L added in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality: Ca
2+105mg/L, total alkalinity 123mg/L, Cl
-26mg/L, SO
4 2-33mg/L, pH8.1, turbidity 3.6mg/L.Test temperature is 25 ℃, and test period is 40 hours, and test-results sees Table 1.
Embodiment 8
Process for preparation: preparation 100g prefilming agent
5g phosphoric acid is mixed with the 4.5g primary zinc phosphate, stirring and dissolving, adding 1.0g benzotriazole, 8g active ingredient then respectively and be the see acid, 15g active ingredient of 50% diethylenetriamine five methenes is that 50% HEDP, 30g solid content are 30% AA/HPA multipolymer (weight ratio is AA/HPA=70/30), be dissolved in the 36.5g water, stir fully dissolving, shake up, promptly obtain the 100g liquid medicine of required preparation.By weight percentage, wherein:
Phosphoric acid 5.0%
Primary zinc phosphate 4.5%
Organic phospho acid 11.5%
Benzotriazole 1.0%
Contain carboxylic acid-based copolymer 9.0%
Water 69.0%
The drug concentration of the above-mentioned prefilming agent for preparing by 400mg/L added in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality: Ca
2+105mg/L, total alkalinity 123mg/L, Cl
-26mg/L, SO
4 2-33mg/L, pH8.1, turbidity 3.6mg/L.Test temperature is 25 ℃, and test period is 35 hours, and test-results sees Table 1.
Comparative Examples 1
PH with thionamic acid control test water is 5.5-6.5, drug concentration by Sodium hexametaphosphate 99 160mg/L, zinc sulfate 40mg/L and AA/MA/HPA multipolymer (weight ratio is AA/MA/HPA=70/15/15) 48mg/L adds in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality: Ca
2+135mg/L, total alkalinity 123mg/L, Cl
-46mg/L, SO
4 2-24mg/L, pH8.4, turbidity 3.6mg/L.Test temperature is 30 ℃, and test period is 24 hours, and test-results sees Table 1.
Comparative Examples 2
Pre-film adds in test water by the drug concentration of PAPE 350mg/L, zinc sulfate 6mg/L and AA/MA/HPA multipolymer (weight ratio is AA/MA/HPA=70/15/15) 60mg/L, carry out " rotary hanging plate weight-loss method " test, test water water quality: Ca
2+155mg/L, total alkalinity 123mg/L, Cl
-106mg/L, SO
4 2-34mg/L, pH8.4, turbidity 1.6mg/L.Test temperature is 25 ℃, and test period is 24 hours, and test-results sees Table 1.
Comparative Examples 3
Pre-film adds in test water by the drug concentration of PAPE 350mg/L, zinc sulfate 6mg/L and AA/MA/HPA multipolymer (weight ratio is AA/MA/HPA=70/15/15) 60mg/L, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+231mg/L, total alkalinity 243mg/L, Cl
-79mg/L, SO
4 2-135mg/L, pH8.1, turbidity 1.6mg/L.Test temperature is 40 ℃, and test period is 14 hours, and test-results sees Table 1.
Comparative Examples 4
Pre-film is controlled pH5.5-6.5 with thionamic acid, drug concentration by Sodium hexametaphosphate 99 160mg/L, zinc sulfate 80mg/L and AA/MA/HPA multipolymer (weight ratio is AA/MA/HPA=70/15/15) 48mg/L adds in test water, carry out " rotary hanging plate weight-loss method " test, test water water quality is: Ca
2+105mg/L, total alkalinity 123mg/L, Cl
-26mg/L, SO
4 2-33mg/L, pH8.1, turbidity 3.6mg/L.Test temperature is 25 ℃, and test period is 40 hours, and test-results sees Table 1.
Table 1
| Embodiment | The copper sulfate developing time, s | Corrosion of carbon steel speed (mm/a) |
| Embodiment 1 | 140 | 0.014 |
| Embodiment 2 | 138 | 0.016 |
| Embodiment 3 | 135 | 0.018 |
| Embodiment 4 | 132 | 0.019 |
| Embodiment 5 | 157 | 0.024 |
| Embodiment 6 | 144 | 0.023 |
| Embodiment 7 | 129 | 0.017 |
| Embodiment 8 | 161 | 0.012 |
| Comparative Examples 1 | 83 | 0.034 |
| Comparative Examples 2 | 70 | 0.029 |
| Comparative Examples 3 | 75 | 0.037 |
| Comparative Examples 4 | 85 | 0.043 |
By the data of the foregoing description and Comparative Examples as can be seen: the thickness of prefilming agent of the present invention is greater than Comparative Examples; Corrosion of Carbon Steel speed is low, illustrates that also the pre-film effect of prefilming agent of the present invention is good; When testing with prefilming agent of the present invention, need not add sour adjust pH, be the very wide prefilming agent of a kind of use range.
Claims (9)
1. prefilming agent that is suitable for recirculating cooling water system, it is characterized in that described prefilming agent by phosphoric acid, primary zinc phosphate, contain carboxylic acid-based copolymer, organic phospho acid, benzotriazole and water and form, their proportioning is by weight percentage
Phosphoric acid 2-10%
Primary zinc phosphate 1-10%
Organic phospho acid 5-18%
Benzotriazole 0.5-2.0%
Contain carboxylic acid-based copolymer 4.5-10.5%
Water surplus.
2. prefilming agent according to claim 1, it is characterized in that described organic phospho acid is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), the 2-phosphonate group-1 of being selected from, 2,4-butane tricarboxylate (PBTCA), hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids.
3. prefilming agent according to claim 1 is characterized in that the described carboxylic acid-based copolymer of containing is selected from toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid (AA)/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, vinylformic acid/vinyl 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-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, the acrylic acid/esters multipolymer.
4. prefilming agent according to claim 3 is characterized in that described acrylate is selected from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate (HPA).
5. the prefilming method of a recirculating cooling water system, it is characterized in that before the equipment and pipeline normal operation input of recirculating cooling water system, add each described prefilming agent of claim 1-4 in recirculated cooling water, add-on is 200-600mg prefilming agent/L water.
6. the prefilming method of recirculating cooling water system according to claim 5, the calcium ion concn that it is characterized in that described recirculated cooling water is that 80-300mg/L, turbidity are less than 10mg/L.
7. the prefilming method of recirculating cooling water system according to claim 6, when it is characterized in that the recirculated cooling water calcium ion concn greater than 150mg/L, to contain benzotriazole and organic phosphine aqueous acid-abbreviation A liquid earlier and add in the recirculating cooling water system, and in recirculating cooling water system, add phosphoric acid, primary zinc phosphate again and contain the aqueous solution-abbreviation B liquid of carboxylic acid-based copolymer.
8. according to the prefilming method of each described recirculating cooling water system of claim 5-7, the temperature range that it is characterized in that described recirculated cooling water is a room temperature to 50 ℃.
9. according to the prefilming method of each described recirculating cooling water system of claim 5-7, it is characterized in that preliminary filming time is 5-48 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021585806A CN1202028C (en) | 2002-12-26 | 2002-12-26 | Pretreatment filming agent and pretreatment filming method for circulating cooling water system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021585806A CN1202028C (en) | 2002-12-26 | 2002-12-26 | Pretreatment filming agent and pretreatment filming method for circulating cooling water system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1509996A CN1509996A (en) | 2004-07-07 |
| CN1202028C true CN1202028C (en) | 2005-05-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021585806A Expired - Lifetime CN1202028C (en) | 2002-12-26 | 2002-12-26 | Pretreatment filming agent and pretreatment filming method for circulating cooling water system |
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| CN (1) | CN1202028C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105112902A (en) * | 2015-08-25 | 2015-12-02 | 河北钢铁股份有限公司承德分公司 | Passivation method for circulating water box |
| CN107806847B (en) * | 2017-10-26 | 2020-07-07 | 西南石油大学 | Corrosion inhibitor pre-film thickness testing device and method |
| CN108085665B (en) * | 2017-12-30 | 2020-02-07 | 仙桃市信达化工有限责任公司 | Novel industrial circulating cold water system prefilming agent and preparation method thereof |
| CN108623020A (en) * | 2018-05-11 | 2018-10-09 | 西安晶达化工有限公司 | A kind of novel corrosion-retarding antisludging agent and the preparation method and application thereof |
| CN109607833A (en) * | 2018-12-24 | 2019-04-12 | 廊坊萍锅炉保养工程有限公司 | A kind of formula and its application method of corrosion inhibiting and descaling agent |
| CN111441058A (en) * | 2020-05-19 | 2020-07-24 | 北京可林维尔化工有限公司 | Descaling rust-removing corrosion-inhibition prefilming agent and preparation method and application thereof |
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2002
- 2002-12-26 CN CNB021585806A patent/CN1202028C/en not_active Expired - Lifetime
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| CN1509996A (en) | 2004-07-07 |
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