CN100509654C - Low-phosphorus composite antiincrustation corrosion inhibitor and use for water treatment - Google Patents
Low-phosphorus composite antiincrustation corrosion inhibitor and use for water treatment Download PDFInfo
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- CN100509654C CN100509654C CNB2004100736666A CN200410073666A CN100509654C CN 100509654 C CN100509654 C CN 100509654C CN B2004100736666 A CNB2004100736666 A CN B2004100736666A CN 200410073666 A CN200410073666 A CN 200410073666A CN 100509654 C CN100509654 C CN 100509654C
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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
-
- 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
-
- 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
- C23F11/10—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 using organic inhibitors
-
- 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
- C23F11/10—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 using organic inhibitors
- C23F11/173—Macromolecular compounds
Abstract
This invention relates to a sort of low-phosphor scale-corrosion inhibitor which includes PBTCA, (and/or HPAA), poly-aspartic acid and/or polyepoxysuccinic acid and carboxyl-containing polymer. This inhibitor can be used to treat recirculated cooling water in ways such as inhibiting the forming of CaCO3 scale, inhibiting corrosion and stabilizing Zn2+ in 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
In recirculating cooling water system, mainly exist fouling, corrosion and microorganism to endanger three aspect problems.Anti-locking system fouling and corrosion most convenient and effective means are to add corrosion inhibiting and descaling agent in recirculated cooling water.The at present domestic prescription that is usually used in the recirculated cooling water processing mostly is phosphine system prescription, and its host is for containing phosphonate group (-PO
3H
2) the direct corrosion inhibiting and descaling agent that links to each other with carbon atom, often be referred to as organic phospho acid.They mainly comprise: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic (DEPTMP) etc.
Organic phospho acid has made water technology and technology that considerable progress arranged since the later stage in the sixties is developed and is applied to the recirculated cooling water processing.Compare with the inorganic polyphosphate in the early stage phosphorus line formulation, organic phospho acid have good chemical stability, not facile hydrolysis, can anti-comparatively high temps, dosing is little, and has inhibition concurrently and scale inhibition is difunctional.Organic phospho acid is a class cathode type inhibiter, is again class equivalent Scale inhibitors non-chemically simultaneously, has tangible molten limit effect.They are to many metal ions such as Ca
2+, Mg
2+, Cu
2+, Zn
2+Deng all having good sequestering power, even to the inorganic salts such as the CaCO of some metals
3, CaSO
4, MgSiO
3Deng deactivation is preferably also arranged.But organic phosphine commonly used can not suppress calcium phosphate scale and zinc dirt effectively and solve the iron oxide precipitation problem, and itself easily is formed with the machine phosphonic acid dirt.In addition, 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, the environmental administration of many countries has put into effect the discharging that corresponding regulations limits P contained compound, for example Germany has required the discharging of phosphorus smaller or equal to 1mg/L, and the content of organic phosphine prescription phosphorus in recirculated water commonly used is generally at 4-10mg/L, and the application of organic phosphine therefore commonly used will be restricted.
Summary of the invention
2-phosphonic acid butane-1,2,4-tricarboxylic acid (being 2-phosphonate group-1,2,4-butane tricarboxylate, PBTCA) and 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA) have the low advantage of phosphorus content; And poly aspartic acid and/or poly-epoxy succinic acid and contain carboxylic acid-based copolymer's dirt dispersion agent and have and suppress calcium phosphate scale, zinc dirt effectively and disperse the lime carbonate performance, remedied the deficiency of organic phosphine class medicament commonly used, itself and the composite consumption that reduces PBTCA, HPAA of PBTCA, HPAA are applied to circulating water treatment and can reduce organic phosphine medicament commonly used because of the high harm to environment of phosphorus content.
The object of the present invention is to provide a kind of 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, can reduce simultaneously and use the organic phosphine medicament always because of of the harm of phosphorus content height 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 and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, poly aspartic acid and contain that the carboxylic acid group polymer forms, or by 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, poly-epoxy succinic acid and contain that the carboxylic acid group polymer forms, or by 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, poly aspartic acid, poly-epoxy succinic acid and contain that the carboxylic acid group polymer forms, the wherein said carboxylic acid group polymer of containing is at least a polyacrylic acid that is selected from, polymaleic anhydride, vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer (T225), vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, maleic anhydride/styrene sulfonic acid multipolymer, toxilic acid/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic 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; The described carboxylic acid group polymer of containing has only when a kind of, and it can only be multipolymer.
Composite scale-inhibiting corrosion inhibitor of the present invention is respectively with respect to the effective concentration of pending each component of aqueous solution total amount: 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid are 1-3mg/L, poly aspartic acid and/or poly-epoxy succinic acid are 2-20mg/L, and containing the carboxylic acid-based copolymer is 2-20mg/L.
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, is 0.5-1.5mg/L with respect to the effective concentration of pending aqueous solution total amount copper material corrosion inhibitor.
For the stronger recirculated cooling water of corrodibility, its inhibition problem should be the major issue that will solve, composite scale-inhibiting corrosion inhibitor of the present invention is being used for recirculated cooling water, and composite scale-inhibiting corrosion inhibitor of the present invention also can contain zinc salt as inhibiter, and described zinc salt is selected from zinc sulfate or zinc chloride.With respect to the effective concentration of pending aqueous solution total amount zinc salt (with Zn
2+Meter) be 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 is less, can 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, contain carboxylic acid-based copolymer, poly aspartic acid and/or poly-epoxy succinic acid, copper material corrosion inhibitor (if any) and zinc salt (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 performance 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.
Low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention can be applicable to recirculated cooling water and handles, and is particularly suitable for being applied to the processing of the not adjust pH recirculated cooling water of medium hardness that calcium hardness and total alkalinity sum are 100-300mg/L, moderate alkalinity water quality.
For calcium hardness and total alkalinity sum is the high rigidity more than the 300mg/L, high basicity water quality, when it is used for recirculated cooling water, for preventing fouling, often adopt to add sour adjust pH, reduce the basicity in the water, at this moment, the inhibition problem should be the major issue that will solve, when composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water, also should increase the good component of corrosion inhibition, as zinc salt etc.
For calcium hardness and total alkalinity sum is the soft below the 100mg/L, low basicity water quality, when it is used for recirculated cooling water, the major issue that solves also is the inhibition problem, equally, when composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water, also should increase the good component of corrosion inhibition, as zinc salt etc.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
The test raw water quality sees Table 1.
Table 1 test raw water quality
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | pH | Specific conductivity | Total molten solid |
| Former water 1 | 97 | 155 | 176 | 14 | 35 | 7.8 | 210 | 315 |
| Former water 2 | 265 | 380 | 370 | 78 | 120 | 7.8 | 1020 | 756 |
| Former water 3 | 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 the low-phosphorous composite scale-inhibiting corrosion inhibitor of following embodiment gained is as follows:
Resistance calcium carbonate scale performance is got the former water of test, adding is by drug concentration that embodiment added, evaporation concentration in 80 ± 1 ℃ of waters bath with thermostatic control, to cycles of concentration (test former water 1 and 3 to 5 times of cycles of concentration, the test former water 2 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 (the former water 1 of concentration test and 3 is to 5 times of multiples, not adjust pH to put into the test water that is added with the drug concentration that adds by embodiment; The former water 2 of concentration test is to 2 times of multiples, and adjust pH) in, 40 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72 hours, and 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 * △ 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 0.078dl/g 30 ℃ the time to take by weighing the 4.0g effective content and be 50% PBTCA, 5.0g solid content and be 40% poly aspartic acid, 60.0g solid content and be 30% T225, weight ratio is AA/HPA=80/20), add 31.0g water, shake up, promptly obtain the 100.0g medicament of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the medicament for preparing, the effective concentration of PBTCA, poly aspartic acid, T225 is respectively 2mg/L, 2mg/L, 18mg/L in the water, and 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, 50.0g solid content and be 40% poly-epoxy succinic acid and 30.0g solid content and be 30% AA/AMPS contains carboxylic acid group and sulfonic group copolymer simultaneously (limit viscosity number is 0.074dl/g 30 ℃ the time, weight ratio is AA/AMPS=70/30), join in the 15.0g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that HPAA, poly-epoxy succinic acid, AA/AMPS contain carboxylic acid group and sulfonic group copolymer simultaneously in the water is respectively 2mg/L, 20mg/L, 9mg/L, and total phosphorus is (with PO in the water
4 3-Meter) be 0.9mg/L.
Embodiment 3
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 6.0g effective content and be 50% PBTCA, 20.0g solid content and be 40% poly aspartic acid, 10.0g solid content and be 40% poly-epoxy succinic acid and 26.7g solid content and be 30% T225, weight ratio is AA/HPA=80/20), join in the 37.3g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of PBTCA, poly aspartic acid, poly-epoxy succinic acid, T225 is respectively 3mg/L, 8mg/L, 4mg/L, 8mg/L in the water, and total phosphorus is (with PO in the water
4 3-Meter) be 0.7mg/L.
Embodiment 4
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 5.0g effective content and be 50% PBTCA, 10.0g solid content and be 40% poly-epoxy succinic acid, 13.3g solid content and be 30% polyacrylic acid (30 ℃ time the limit viscosity number be 0.072dl/g) and 30.0g solid content and be 30% T225, weight ratio is AA/HPA=80/20), join in the 41.7g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of PBTCA, poly-epoxy succinic acid, polyacrylic acid, T225 is respectively 2.5mg/L, 4mg/L, 4mg/L, 9mg/L in the water, and total phosphorus is (with PO in the water
4 3-Meter) be 0.9mg/L.
Embodiment 5
Take by weighing the 2.5g effective content and be 40% HPAA, 3.0g effective content is 50% PBTCA, 15.0g solid content is 40% poly aspartic acid, 10.0g solid content is 40% poly-epoxy succinic acid, solid content is 30% T225, and (limit viscosity number is 0.072dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 20.0g and AA/AMPS contain carboxylic acid group and sulfonic group copolymer simultaneously (limit viscosity number be 0.074dl/g 30 ℃ the time, weight ratio is AA/AMPS=70/30) 16.7g, join in the water of 32.8g, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that HPAA, PBTCA, poly aspartic acid, poly-epoxy succinic acid, T225, AA/AMPS contain carboxylic acid group and sulfonic group copolymer simultaneously in the water is respectively 1mg/L, 1.5mg/L, 6mg/L, 4mg/L, 6mg/L, 5mg/L, and total phosphorus is (with PO in the water
4 3-Meter) be 1.0mg/L.
Embodiment 6
Taking by weighing the 4.0g effective content and be 40% HPAA, 10.0g solid content and be 40% poly aspartic acid, 10.0g solid content and be 40% poly-epoxy succinic acid, 14.0g solid content is 50% polymaleic anhydride (the averagemolecular wt amount is 680), (limit viscosity number is 0.072dl/g to the T225 of 15.0g30% 30 ℃ the time, weight ratio is AA/HPA=80/20), join in the 47.0g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of HPAA, poly aspartic acid, poly-epoxy succinic acid, polymaleic anhydride, T225 is respectively 1.6mg/L, 4mg/L, 4mg/L, 7mg/L, 4.5mg/L in the water, and total phosphorus is (with PO in the water
4 3-Meter) be 0.8mg/L.
Embodiment 7
Take by weighing the 4.0g effective content and be 40% HPAA, 10.0g solid content is 40% poly aspartic acid, 10.0g solid content is 40% poly-epoxy succinic acid, 14.0g solid content is 50% polymaleic anhydride (the averagemolecular wt amount is 680), 15.0g solid content is 30% polyacrylic acid (30 ℃ time the limit viscosity number be 0.072dl/g), (limit viscosity number is 0.072dl/g 30 ℃ the time 15.0g solid content is 30% T225, weight ratio is AA/HPA=80/20) and 15.0g AA/AMPS contains carboxylic acid group and sulfonic group copolymer simultaneously, and (limit viscosity number is 0.074dl/g 30 ℃ the time, weight ratio is AA/AMPS=70/30), join in the 17.0g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that HPAA, poly aspartic acid, poly-epoxy succinic acid, polymaleic anhydride, polyacrylic acid, T225 and AA/AMPS contain carboxylic acid group and sulfonic group copolymer simultaneously in the water is respectively 1.6mg/L, 4mg/L, 4mg/L, 7mg/L, 4.5mg/L, 4.5mg/L, 4.5mg/L, and total phosphorus is (with PO in the water
4 3-Meter) be 0.8mg/L.
Embodiment 8
(limit viscosity number is 0.072dl/g 30 ℃ the time to take by weighing the 5.0g effective content and be 40% HPAA, 15.0g solid content and be 40% poly aspartic acid, 10.0g solid content and be 40% poly-epoxy succinic acid, solid content and be 30% T225, weight ratio is AA/HPA=80/20) 20.0g and 4.4g Zinc vitriol, join in the water of 45.6g, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in former water 2 (with sulfuric acid adjust pH 7.8-8.2) and former water 3 by the drug concentration of 100mg/L with the liquid medicine for preparing, HPAA, poly aspartic acid, poly-epoxy succinic acid, T225, Zn in the water
2+Effective concentration be respectively 2mg/L, 6mg/L, 4mg/L, 6mg/L, 1mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 0.8mg/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% PBTCA9.0g, HEDP 9.0g, add in the 42.0g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of the terpolymer of AA/AMPS/HPA, PBTCA, HEDP is respectively 12mg/L, 4.5mg/L, 4.5mg/L, and total phosphorus is (with PO in the water
4 3-Meter) be 6.1mg/L.
Comparative Examples 2
(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 2.1g Zinc Chloride Anhydrous, add in the 39.9g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test 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, 1mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 6.1mg/L.
Comparative Examples 3
Process for preparation: the phosphorous liquid medicine of preparation 100.0g
Take by weighing the 20.0g solid content and be 40% poly aspartic acid, active ingredient and be 50% PBTCA 12.0g and HEDP12.0g and join in the 56.0g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of poly aspartic acid, PBTCA, HEDP is respectively 8mg/L, 6mg/L, 6mg/L in the water, and total phosphorus is (with PO in the water
4 3-Meter) be 8.3mg/L.
Comparative Examples 4
Process for preparation: preparation 100.0g is phosphorous, contain the zinc salt liquid medicine
Take by weighing the 20.0g solid content and be 40% poly-epoxy succinic acid, active ingredient and be 50% PBTCA 12.0g and HEDP12.0g, 4.4g Zinc vitriol and join in the 51.6g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in test former water 2 (with sulfuric acid adjust pH 7.8-8.2) and former water 3 by the drug concentration of 100mg/L with the liquid medicine for preparing, poly-epoxy succinic acid, PBTCA, HEDP, Zn in the water
2+Effective concentration be respectively 8mg/L, 6mg/L, 6mg/L, 1mg/L, total phosphorus is (with PO in the water
4 3-Meter) be 8.3mg/L.
Comparative Examples 5
Process for preparation: preparation 100.0g liquid medicine
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 2.0g effective content and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), 10.0g solid content and be 40% poly-epoxy succinic acid, 13.3g solid content and be 30% polyacrylic acid (30 ℃ time the limit viscosity number be 0.072dl/g) and 30.0g solid content and be 30% T225, weight ratio is AA/HPA=80/20), join in the 44.7g water, shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of HEDP, poly-epoxy succinic acid, polyacrylic acid, T225 is respectively 1mg/L, 4mg/L, 4mg/L, 9mg/L in the water, and total phosphorus is (with PO in the water
4 3-Meter) be 1.0mg/L.
Carry out static test by the above-mentioned concentration that adds, inhibition and scale inhibition effect see Table 2.
The inhibition of table 2 medicament and scale inhibition effect
Table 2 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.Can reduce simultaneously the content of total phosphorus in the recirculated cooling water.
Embodiment 9
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.
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 3
The compound of B tower: embodiment 4
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality sees Table 1 former water 1.
The dynamic analog test test tube the results are shown in Table 3.
Table 3 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, using low-phosphorous composite scale-inhibiting corrosion inhibitor 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 0.031mm/a, reach China Petrochemical Industry's " good level " standard, adhere to speed 4.2mcm, reach " fine level " standard, be better than inhibition and the scale inhibition of Comparative Examples prescription when calcium hardness+total alkalinity is 950 ± 50mg/L.
Claims (9)
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, poly aspartic acid and contain that the carboxylic acid group polymer forms, or by 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, poly-epoxy succinic acid and contain that the carboxylic acid group polymer forms, or by 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, poly aspartic acid, poly-epoxy succinic acid and contain that the carboxylic acid group polymer forms, the wherein said carboxylic acid group polymer of containing is at least a polyacrylic acid that is selected from, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, maleic anhydride/styrene sulfonic acid multipolymer, toxilic acid/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic 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; The described carboxylic acid group polymer of containing has only when a kind of, and it can only be multipolymer.
2. anti-incrustation corrosion inhibitor according to claim 1, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: 2-phosphonic acid butane-1,2,4-tricarboxylic acid and/or 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid are 1-3mg/L, poly aspartic acid and/or poly-epoxy succinic acid are 2-20mg/L, and containing the carboxylic acid-based copolymer is 2-20mg/L.
3. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that described anti-incrustation corrosion inhibitor also contains heterogeneous ring compound as copper material corrosion inhibitor.
4. anti-incrustation corrosion inhibitor according to claim 3 is characterized in that described copper material corrosion inhibitor selected from mercapto benzothiazole and benzotriazole.
5. anti-incrustation corrosion inhibitor according to claim 3 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.
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 zinc salt.
7. anti-incrustation corrosion inhibitor according to claim 6 is characterized in that described zinc salt is selected from zinc sulfate or zinc chloride.
8. 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 0.5-1.5mg/L.
9. the application of each described anti-incrustation corrosion inhibitor of claim 1-8 is characterized in that each described anti-incrustation corrosion inhibitor of claim 1-8 is applicable to the recirculated cooling water processing.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866032A (en) * | 1995-11-01 | 1999-02-02 | Betzdearborn Inc. | Composition for controlling scale formation in aqueous systems |
| CN1323750A (en) * | 2001-06-19 | 2001-11-28 | 华东理工大学 | Composite water treating agent with polyasparagic acid as main component |
| CN1339015A (en) * | 1999-01-28 | 2002-03-06 | 阿什兰公司 | Scale and/or corrosion inhibiting composition |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
| CN1417139A (en) * | 2001-11-08 | 2003-05-14 | 北京燕山石油化工公司研究院 | Method for reusing ammonia nitrogen containing effluent as circular cooling water |
| CN1417138A (en) * | 2001-11-08 | 2003-05-14 | 北京燕山石油化工公司研究院 | Composite scale-inhibiting corrosion inhibitor suitable for reusing ammonia nitrogen containing effluent as circular cooling water |
| CN1438185A (en) * | 2003-01-25 | 2003-08-27 | 王海宁 | Green scale corrosion inhibitor |
| CN1463935A (en) * | 2002-06-07 | 2003-12-31 | 川化集团有限责任公司 | Environment-friendly water quality stabilizer |
| CN1491907A (en) * | 2002-10-23 | 2004-04-28 | 中国石油化工股份有限公司北京燕山分 | Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water |
-
2004
- 2004-08-31 CN CNB2004100736666A patent/CN100509654C/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866032A (en) * | 1995-11-01 | 1999-02-02 | Betzdearborn Inc. | Composition for controlling scale formation in aqueous systems |
| CN1339015A (en) * | 1999-01-28 | 2002-03-06 | 阿什兰公司 | Scale and/or corrosion inhibiting composition |
| CN1323750A (en) * | 2001-06-19 | 2001-11-28 | 华东理工大学 | Composite water treating agent with polyasparagic acid as main component |
| CN1417139A (en) * | 2001-11-08 | 2003-05-14 | 北京燕山石油化工公司研究院 | Method for reusing ammonia nitrogen containing effluent as circular cooling water |
| CN1417138A (en) * | 2001-11-08 | 2003-05-14 | 北京燕山石油化工公司研究院 | Composite scale-inhibiting corrosion inhibitor suitable for reusing ammonia nitrogen containing effluent as circular cooling water |
| CN1398799A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Prepn of polyasparagic acid as environment protecting scale inhibitor |
| CN1463935A (en) * | 2002-06-07 | 2003-12-31 | 川化集团有限责任公司 | Environment-friendly water quality stabilizer |
| CN1491907A (en) * | 2002-10-23 | 2004-04-28 | 中国石油化工股份有限公司北京燕山分 | Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water |
| CN1438185A (en) * | 2003-01-25 | 2003-08-27 | 王海宁 | Green scale corrosion inhibitor |
Non-Patent Citations (6)
| Title |
|---|
| 绿色水处理剂聚环氧琥珀酸的研究进展. 秦会敏.石化技术，第10卷第4期. 2003 |
| 绿色水处理剂聚环氧琥珀酸的研究进展. 秦会敏.石化技术，第10卷第4期. 2003 * |
| 聚天冬氨酸衍生物的合成及性能研究. 高利军.石油化工，第32卷第9期. 2003 |
| 聚天冬氨酸衍生物的合成及性能研究. 高利军.石油化工，第32卷第9期. 2003 * |
| 聚环氧琥珀酸的阻垢缓蚀性能研究. 吕志芳.工业水处理，第21卷第3期. 2001 |
| 聚环氧琥珀酸的阻垢缓蚀性能研究. 吕志芳.工业水处理，第21卷第3期. 2001 * |
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