CN102452725A - Composite scale and corrosion inhibitor and its application - Google Patents
Composite scale and corrosion inhibitor and its application Download PDFInfo
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- CN102452725A CN102452725A CN2010105124619A CN201010512461A CN102452725A CN 102452725 A CN102452725 A CN 102452725A CN 2010105124619 A CN2010105124619 A CN 2010105124619A CN 201010512461 A CN201010512461 A CN 201010512461A CN 102452725 A CN102452725 A CN 102452725A
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- acid
- corrosion inhibitor
- water
- multipolymer
- composite scale
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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
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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
Abstract
The invention relates to a composite scale and corrosion inhibitor and its application. The composite scale and corrosion inhibitor comprises a water-soluble borate, at least one organic phosphonic acid and at least one scale inhibition and dispersion agent which is a carboxyl-containing polymer. With good comprehensive performance, excellent CaCO3 scale inhibition function, and good ability to stabilize Zn<2+> in water, as well as corrosion inhibition property, the composite scale and corrosion inhibitor of the invention is suitable for treatment of circulating cooling water treatment and has low organic phosphonic acid consumption, thus reducing damage to environment by phosphorus discharge as well as borate consumption simultaneously.
Description
Technical field
The present invention relates to a kind of composite scale-inhibiting corrosion inhibitor and application thereof, relate in particular to a kind of composite scale-inhibiting corrosion inhibitor and the application in recirculated cooling water is handled thereof of boracic hydrochlorate.
Background technology
Along with China's rapid development of economy, source material type water shortage problem becomes increasingly conspicuous.There is more than 400 urban water shortage in China at present, and normal time lack of water reaches 60 * 10
8m
3, expectation the year two thousand thirty water deficit will reach (400-500) * 10
8m
3Well-known petroleum chemical enterprise water consumption is big, and wherein the recirculated cooling water consumption accounts for 80% of total industrial water consumption, and for saving medicinal water, one of them method is to promote cycles of concentration, but this certainly will increase the difficulty of administering fouling, corrosion and microbiological manipulation.Anti-locking system fouling is in recirculated cooling water, to add corrosion inhibiting and descaling agent with corrosion most convenient and effective means.Mostly the at present domestic prescription that is usually used in the recirculated cooling water processing is the organic phospho acid prescription.Organic phospho acid have good chemicalstability, not facile hydrolysis, can anti-comparatively high temps, and have inhibition concurrently and scale inhibition is difunctional.Though the consumption of organic phospho acid is little, the working concentration in recirculated water is merely 4-10mg/L, and phosphorus content is still higher.The red tide that China's Coastal Areas took place frequently and on a large scale in recent years is relevant with nutraceutical dischargings such as a large amount of phosphorus, nitrogen, has caused huge disaster to aquatic products breed and natural, ecological.P contained compound makes people recognize the importance of control P contained compound discharging gradually to the pollution of water body and the eutrophication problem that causes.Simultaneously, low-phosphorous, phosphate-free water treatment agent has become the focus of research.The consumption that how when guaranteeing its corrosion and scale inhibition performance of organic phospho acid performance, to reduce organic phospho acid again is the problem that needs research.
Li Lu etc. (" application of poly-epoxy succinic acid in the blast furnace recirculated cooling water "; Process water and waste water; 2006,37 (6): 68-70) discover: by 12mg/L poly-epoxy succinic acid, 8mg/L 2-phosphonate group-1,2; The corrosion inhibiting and descaling agent that 4-butane tricarboxylate (PBTCA), 4mg/L zinc salt, 4mg/L poly-hydroxy ethers zinc stabilizer (TJWD105) are formed can make Corrosion rate in Carbon Steel be lower than 0.05mm/a.Its shortcoming is that high being prone to of organic phosphine consumption works the mischief to environment.CN101353205A discloses a kind of method that prevents the soft water etching apparatus, and its characteristics are, in softening water, add borate and copper inhibitor, and the borate dosage is between 1200-2000mg/L, and the copper inhibitor dosage is between 1-2mg/L.At blast furnace furnace wall, when the hotblast stove recirculated cooling water adopts softening water, select for use this prescription can prevent softening water to corrosion on Equipment, its shortcoming is that the borate consumption is too big.
Summary of the invention
The contriver discovers: the composite scale-inhibiting corrosion inhibitor that contains borate, organic phospho acid and dirt dispersion agent can suppress calcium phosphate scale, zinc dirt effectively and disperse the lime carbonate performance, when being applied to circulating water treatment, can reduce the consumption of borate and organic phospho acid.
The object of the present invention is to provide a kind of composite scale-inhibiting corrosion inhibitor.
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 composite scale-inhibiting corrosion inhibitor, it comprises a kind of water-soluble borate, at least a organic phospho acid and at least a dirt dispersion agent, and said dirt dispersion agent is for containing the carboxylic acid group polymer.
Borate of the present invention is selected from Sodium Tetraborate and potassium borate, and sylvite is higher than the sodium salt price, considers from economic angle, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees.
Organic phospho acid of the present invention is selected from HEDP, ATMP, 2-phosphonate group-1; 2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycocoll two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids and polyether-based polyamino methylene phosphonic acid.
According to the inventionly contain the carboxylic acid group polymer for homopolymer, copolymer or terpolymer, preferably from SAP 73, poly-epoxy succinic acid, ROHM, HPMA, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, propenoate/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 and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said propenoate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
With respect to pending aqueous solution total amount, the effective concentration of each component is: borate is (with B
4O
7 2-Meter) be 20-60mg/L, organic phosphine 2-4mg/L, containing carboxylic acid group polymer's concentration is 2-20mg/L.
When in recirculating cooling water system, using copper material equipment; Composite scale-inhibiting corrosion inhibitor 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.
When composite scale-inhibiting corrosion inhibitor of the present invention is used for recirculated cooling water, also can contain zinc salt as inhibiter, said zinc salt is selected from zinc sulfate or zinc chloride.With respect to pending aqueous solution total amount, the effective concentration of zinc salt is (with Zn
2+Meter) be 0.5-3.0mg/L.
Available ordinary method prepares composite scale-inhibiting corrosion inhibitor; The reinforced order of each component is unimportant; For example can be with organic phosphoric acid, contain carboxylic acid group polymer, borate, zinc salt (if any) and copper material corrosion inhibitor (if any) and water by predetermined mixed, can make required composite scale-inhibiting corrosion inhibitor.
Composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3The dirt performance also has Zn in the good stabilize water
2+Ability and corrosion inhibition, be applicable to that recirculated cooling water handles.In addition, the consumption of organic phospho acid is few in the composite scale-inhibiting corrosion inhibitor of the present invention, can reduce the harm of phosphorus discharging to environment; Simultaneously, also can reduce boratory consumption.
Composite scale-inhibiting corrosion inhibitor of the present invention is particularly suitable for being applied to calcium hardness and the total alkalinity sum is that the soft less than 100mg/L, low basicity water quality and calcium hardness and total alkalinity sum are the high firmness more than the 300mg/L, the processing that adds sour adjust pH recirculated cooling water of high basicity water quality.
Embodiment
Following embodiment will help to explain the present invention, but not limit to its scope.
The used test raw water quality of following embodiment 1-9 and Comparative Examples 1-4 is seen table 1.
Table 1 test raw water quality
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | pH | Specific conductivity | Total dissolving admittedly |
| Test former water 1 | 257 | 384 | 365 | 81 | 123 | 7.8 | 1020 | 759 |
| Test former water 2 | 23 | 34 | 39 | 8 | 13 | 7.4 | 122 | 71 |
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.
The measuring method of water quality is following:
Ca
2+: GB/T 6910-2006 " the mensuration complexometry of BW and water coolant analytical procedure calcium "
Total alkalinity: GB/T 15451-2006 " mensuration of industrial circulating cooling water total alkali and phenolphthalein alkalinity "
Total hardness: GB/T 6909-2008 " mensuration of BW river water coolant analytical procedure hardness "
Cl
-: GB/T 15453-2008 " mensuration of cl ions in industrial circulating cooling water and the BW "
SO
4 2-: GB/T 14642-2009 " the mensuration ion chromatography of fluorine, chlorine, phosphate radical, nitrite anions, nitrate radical and sulfate radical in industrial circulating cooling water and the feedwater "
PH value: GB/T 6920-1986 " the mensuration glass electrode method of water pH value "
Specific conductivity: GB/T 6908-2008 " mensuration of BW river water coolant analytical procedure specific conductivity "
Total dissolving admittedly: GB/T 14415-2007 " mensuration of solid matter in industrial circulating cooling water and the BW "
Zn
2+: GB/T 10656-2008 " the mensuration zincon spectrophotometry of BW and water coolant analytical procedure zine ion "
The assessment of performance method of the composite scale-inhibiting corrosion inhibitor of following embodiment gained is following:
Test water concentrates behind the corresponding multiple laboratory according to raw water quality and prepares voluntarily and obtain, and test water water quality is seen table 2.
Table 2 test water water quality
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- |
| Test water 1 (concentrating 3 times) | 771 | 1152 | 1095 | 243 | 369 |
| Test water 2 (concentrating 5 times) | 115 | 170 | 195 | 40 | 65 |
Resistance calcium carbonate scale performance is got test water, adds by the drug concentration that embodiment added, and in 80 ± 1 ℃ of waters bath with thermostatic control, leaves standstill 10h with the volumetric flask method, remains Ca in the sampling analysis water after cooling
2+Concentration, do blank simultaneously, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Ca
2+Concentration (mg/L)
C
0: the Ca of blank
2+Concentration (mg/L)
C
1: the Ca in the test water
2+Concentration (mg/L)
Stablize the zinc salt performance and get zero(ppm) 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, leave standstill 10h, remain Zn in the sampling analysis water by the drug concentration that embodiment added
2+Concentration, do blank simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Zn
2+Concentration (mg/L)
C
0: the Zn of blank
2+Concentration (mg/L)
C
1: 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 explain 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 appearance; Put into the test water that is added with the drug concentration that adds by embodiment, 45 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72h; The weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=(C * Δ W)/(A * T * ρ)
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10
7
Δ 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)
When measuring scale-inhibiting properties, following embodiment and Comparative Examples are used all adjust pHs not of any test water quality; When measuring corrosion inhibition, need adjust pH when following embodiment and Comparative Examples use-testing water 1.
Embodiment 1
Take by weighing the 135.1g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 5.0g solid content is 50% 2-phosphonate group-1; 2; 4-butane tricarboxylate and 60.0g solid content are that vinylformic acid/styrene sulfonic acid multipolymer of 30% (limit viscosity number is 0.078dl/g 30 ℃ the time, vinylformic acid/styrene sulfonic acid=70/30 (weight ratio, down with)) joins in the 49.9g water; Shake up, promptly obtain the 250.0g medicament of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.0) and 2 by the drug concentration of 250mg/L with the medicament for preparing, B in the water
4O
7 2-, 2-phosphonate group-1,2, the effective concentration of 4-butane tricarboxylate, vinylformic acid/styrene sulfonic acid multipolymer is respectively 55mg/L, 2.5mg/L, 18mg/L.
Embodiment 2
Take by weighing the 98.3g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 7.0g solid content is that 50% ATMP and 32.0g solid content are that 50% HPMA (number-average molecular weight 1000) joins in the 112.7g water, shakes up, and promptly obtains the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 7.9) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, ATMP, HPMA effective concentration be respectively 40mg/L, 3.5mg/L, 16mg/L.
Embodiment 3
Take by weighing 66.3g four hydrations eight Sodium Tetraboratees and (contain B
4O
7 2-37.7%), the 5.0g solid content is that 50% HEDP, 40.0g solid content are that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propanesulfonic acid multipolymer of 30%; Vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propanesulfonic acid=40/30/30) and the 5.3g Zinc Chloride Anhydrous join in the 83.4g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.1) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, HEDP, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propanesulfonic acid multipolymer and Zn
2+Effective concentration is respectively 25mg/L, 2.5mg/L, 12mg/L, 2.5mg/L.
Embodiment 4
Take by weighing the 98.3g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 6.0g solid content is that 50% L-glutamic acid two methene phosphonic acids, 30.0g solid content are that 30% ROHM (number-average molecular weight 3000) and 4.4g Zinc vitriol are dissolved in the 111.3g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 7.8) by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, L-glutamic acid two methene phosphonic acids, ROHM and Zn
2+Effective concentration be respectively 40mg/L, 3mg/L, 9mg/L, 1mg/L.
Embodiment 5
Take by weighing 75.0g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 7.0g solid content is that 50% diethylene triamine pentamethylene phosphonic and 16.7g solid content are that (limit viscosity number is 0.072d l/g 30 ℃ the time for vinylformic acid/vinyl sulfonic acid multipolymer of 30%; Vinylformic acid/vinyl sulfonic acid=70/30) is dissolved in the 101.3g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, diethylene triamine pentamethylene phosphonic, vinylformic acid/vinyl sulfonic acid multipolymer effective concentration be respectively 40mg/L, 3.5mg/L, 5mg/L.
Embodiment 6
Take by weighing 93.8g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 6.0g solid content is that 50% glycocoll two methene phosphines, 16.7g solid content are that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/Propylene glycol monoacrylate multipolymer of 30%; AA/HPA=70/30) and the 1.2g benzotriazole be dissolved in the 132.3g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, glycocoll two methene phosphines, vinylformic acid/Propylene glycol monoacrylate multipolymer and benzotriazole effective concentration be respectively 50mg/L, 3mg/L, 5mg/L, 1.2mg/L.
Embodiment 7
Take by weighing 119.4g four hydrations eight Sodium Tetraboratees and (contain B
4O
7 2-37.7%), the 5.0g solid content be 50% thionamic acid two methene phosphonic acids and 33.3g solid content be vinylformic acid/Propylene glycol monoacrylate/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/HPA/AMPS=70/15/15) be dissolved in the 92.3g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, thionamic acid two methene phosphonic acids and vinylformic acid/Propylene glycol monoacrylate/2-methyl-2 '-effective concentration of acrylamido propane sulfonic acid multipolymer is respectively 45mg/L, 2.5mg/L, 10mg/L.
Embodiment 8
Take by weighing 83.0g five hydrate potassium borates and (contain B
4O
7 2-48.0%), the 5.0g solid content be 50% be that (limit viscosity number is 0.072dl/g to 30% methyl acrylate/styrene sulfonic acid multipolymer 30 ℃ the time to two phosphono and sulfonics, 50.0g solid content; Methyl acrylate/styrene sulfonic acid=80/20) and the 4.2g Zinc Chloride Anhydrous be dissolved in the 107.5g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.2) by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, to two phosphono and sulfonics, methyl acrylate/styrene sulfonic acid multipolymer and Zn
2+Effective concentration be respectively 40mg/L, 2.5mg/L, 15mg/L, 2mg/L.
Embodiment 9
Take by weighing 56.3g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 7.0g solid content be 50% ethylene diamine tetra methylene phosphonic acid and 53.3g solid content be vinylformic acid/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/AMPS=70/30) be dissolved in the 133.4g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.0) by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, ethylene diamine tetra methylene phosphonic acid and vinylformic acid/2-methyl-2 '-effective concentration of acrylamido propane sulfonic acid multipolymer is respectively 30mg/L, 3.5mg/L, 16mg/L.
Embodiment 10
Take by weighing 83.3g five hydration potassium tetraborates and (contain B
4O
7 2-48.0%), the 6.0g solid content is 50% 2-phosphonate group-1; 2; 4-butane tricarboxylate, 26.7g solid content are that 30% toxilic acid/allyl sulphonic acid multipolymer (limit viscosity number is 0.072d l/g 30 ℃ the time, toxilic acid/allyl sulphonic acid=80/20) and 26.7g solid content are 30% ROHM (number-average molecular weight is 3000), join in the 107.3g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.2) by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, 2-phosphonate group-1,2,4-butane tricarboxylate, toxilic acid/allyl sulphonic acid multipolymer, polyacrylic effective concentration are respectively 40mg/L, 3mg/L, 8mg/L, 8mg/L.
Embodiment 11
Take by weighing 56.3g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 7.0g solid content is that 50% polyether-based polyamino methylene phosphonic acid, 16.7g solid content are that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/allyl sulphonic acid multipolymer of 30%; Vinylformic acid/allyl sulphonic acid=70/30), the 12.5g solid content is 40% SAP 73 (number-average molecular weight 3000) and 8.8g Zinc Sulphate Heptahydrate; Be dissolved in the 153.3g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, polyether-based polyamino methylene phosphonic acid, vinylformic acid/allyl sulphonic acid multipolymer, SAP 73 and Zn
2+Effective concentration be respectively 30mg/L, 3.5mg/L, 5mg/L, 5mg/L, 2mg/L.
Embodiment 12
Take by weighing the 73.7g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 4.0g solid content is that 50% HEDP, 3.0g solid content are 50% 2-phosphonate group-1; 2; 4-butane tricarboxylate, 26.7g solid content be vinylformic acid/methyl acrylate/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/ methyl acrylate/AMPS=70/15/15), 20.0g solid content are that 40% poly-epoxy succinic acid (number-average molecular weight is 1000) and 0.8g mercaptobenzothiazole are dissolved in the 121.8g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 7.8) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, HEDP, 2-phosphonate group-1; 2,4-butane tricarboxylate, vinylformic acid/methyl acrylate/2-methyl-2 '-effective concentration of acrylamido propane sulfonic acid multipolymer, poly-epoxy succinic acid is respectively 30mg/L, 2mg/L, 1.5mg/L, 8mg/L, 8mg/L, 0.8mg/L.
Embodiment 13
Take by weighing 46.9g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 3.0g solid content be 50% taurine two methene phosphonic acids, 4.0g solid content be 50% HEDP, 30.0g solid content be vinylformic acid/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/AMPS=70/30), the 30.0g solid content is that (limit viscosity number is 0.076dl/g 30 ℃ the time for maleic anhydride/styrene sulfonic acid multipolymer of 30%; Maleic anhydride/styrene sulfonic acid=80/20) and the 5.3g Zinc Chloride Anhydrous be dissolved in the 130.8g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 7.9) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, taurine two methene phosphonic acids, HEDP, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, maleic anhydride/styrene sulfonic acid multipolymer and Zn
2+Effective concentration be respectively 25mg/L, 1.5mg/L, 2mg/L, 9mg/L, 9mg/L, 2.5mg/L.
Embodiment 14
Take by weighing 56.3g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 2.0g solid content is that 50% L-glutamic acid two methene phosphines, 3.0g solid content are that 50% HEDP, 10.0g solid content are that 40% SAP 73 (number-average molecular weight 3000), 10.0g solid content are that 30% ROHM (number-average molecular weight 3000) and 6.0g solid content are that 50% HPMA (number-average molecular weight 1000) is dissolved in the 162.7g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.2) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, L-glutamic acid two methene phosphines, HEDP, SAP 73, ROHM and HPMA effective concentration be respectively 30mg/L, 1mg/L, 1.5mg/L, 4mg/L, 3mg/L, 3mg/L.
Comparative Examples 1
Take by weighing the 20.0g solid content and be vinylformic acid/methyl acrylate/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/ methyl acrylate/AMPS=60/20/20), active ingredient are 50% 2-phosphonate group-1; 2,4-butane tricarboxylate 9.0g, HEDP 9.0g and 4.2g Zinc Chloride Anhydrous join in the 207.8g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.0) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing; Vinylformic acid/methyl acrylate/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, 2-phosphonate group-1; 2,4-butane tricarboxylate, HEDP and Zn
2+Effective concentration be respectively 6mg/L, 4.5mg/L, 4.5mg/L, 2mg/L.
Comparative Examples 2
Take by weighing 112.6g five hydration sodium tetraborates and (contain B
4O
7 2-40.7%), the 50.0g solid content is that 40% poly-epoxy succinic acid (number-average molecular weight 1000) and 4.2g Zinc Chloride Anhydrous join in the 83.2g water, shakes up, and promptly obtains the 250.0g liquid medicine of required preparation.
When adding in test water 1 (using the sulfuric acid adjust pH is 8.1) and 2 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, poly-epoxy succinic acid and Zn
2+Effective concentration be respectively 60mg/L, 20mg/L, 2.0mg/L.
Carry out static test by the above-mentioned concentration that adds, inhibition and scale inhibition effect are seen table 3.Carry out static test by the above-mentioned concentration that adds, inhibition and scale inhibition effect are seen table 3.
The inhibition of table 3 medicament and scale inhibition effect
Table 3 data declaration, 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 satisfactory stability water
2+Ability and corrosion inhibition.
Embodiment 14 and Comparative Examples 3
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-2008 of the People's Republic of China, and controlled variable is following.
Cycles of concentration control is controlled with calcium hardness+total alkalinity value:
Concentrate the A tower: 950 ± 50mg/L B tower, 950 ± 50mg/L
Flow velocity: 1.0m/s
Medicament: A tower: the compound of Comparative Examples 1
The compound of B tower: embodiment 11
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality is seen the former water 1 of table 1.
Dynamic analog test test tube result sees table 4.
Table 4 dynamic analog test test tube result
Regulation among the standard GB 50050-2007 " Code for design of industrial recirculating cooling water treatment ", the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; " the small-sized experimental analogic method of testing laboratory " regulation corrosion of Carbon Steel speed is " fine " level at 0-0.028mm/a in " the water coolant analysis and the TP " of production department of China PetroChemical Corporation and development division establishment; 0.028-0.056mm/a between be " good " level, 0.056-0.070mm/a for " can allow " level; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.
This shows; Using non-Phosphorus composite anti incrustation eorrosion snhibiter of the present invention is under the situation of 950 ± 50mg/L in calcium hardness and total alkalinity sum; The erosion rate of test tube is 0.034mm/a, reaches China Petrochemical Industry's " good level " standard, adheres to speed 6.3mcm; Reach " good level " standard, being better than contrast has inhibition and the scale inhibition of phosphorus prescription when calcium hardness+total alkalinity is 950 ± 50mg/L.
Claims (10)
1. composite scale-inhibiting corrosion inhibitor, it comprises a kind of water-soluble borate, at least a organic phospho acid and at least a dirt dispersion agent, and said dirt dispersion agent is for containing the carboxylic acid group polymer.
2. composite scale-inhibiting corrosion inhibitor according to claim 1 is characterized in that said borate is selected from Sodium Tetraborate and potassium borate, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees.
3. composite scale-inhibiting corrosion inhibitor according to claim 1 and 2; It is characterized in that said organic phospho acid is selected from HEDP, ATMP, 2-phosphonate group-1; 2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycocoll two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids and polyether-based polyamino methylene phosphonic acid.
4. according to each described composite scale-inhibiting corrosion inhibitor of claim 1-3; It is characterized in that containing the carboxylic acid group polymer and be selected from homopolymer, copolymer and terpolymer, preferably from SAP 73, poly-epoxy succinic acid, ROHM, HPMA, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, propenoate/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 and vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said propenoate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
5. according to each described composite scale-inhibiting corrosion inhibitor of claim 1-4, it is characterized in that said anti-incrustation corrosion inhibitor also contains heterogeneous ring compound as copper material corrosion inhibitor, heterogeneous ring compound is preferably from mercaptobenzothiazole and benzotriazole.
6. according to each described composite scale-inhibiting corrosion inhibitor of claim 1-5, it is characterized in that said anti-incrustation corrosion inhibitor also contains zinc salt, preferably from zinc sulfate and zinc chloride.
7. according to each described anti-incrustation corrosion inhibitor of claim 1-6, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: borate is (with B
4O
7 2-Meter) be 20-60mg/L, organic phospho acid is 2-4mg/L, and containing carboxylic acid group polymer's concentration is 2-20mg/L.
8. composite scale-inhibiting corrosion inhibitor according to claim 5 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. anti-incrustation corrosion inhibitor according to claim 6 is characterized in that effective concentration with respect to pending aqueous solution total amount zinc salt is with Zn
2+Count 0.5-3.0mg/L.
10. according to the application of each described composite scale-inhibiting corrosion inhibitor of claim 1-9, it is characterized in that each described composite scale-inhibiting corrosion inhibitor of claim 1-9 is applicable to the recirculated cooling water processing.
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