CN1850661A - Green environment-protective composite slow-corrosion scale resistor for circulated cooling-water treatment - Google Patents
Green environment-protective composite slow-corrosion scale resistor for circulated cooling-water treatment Download PDFInfo
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Abstract
The invention belongs to the environmental protection field, concretely relating to a green environmental-protection composite corrosion inhibition antifouling agent for water circulating cooling, compounded of antifouling dispersants and corrosion inhibitors: polyepoxy sodium succinate, polymerized sodium aspartate, hydrolyzed polymaleic anhydride, sodium gluconate, zinc salt, in the mass ratio of 1-6 to 1-4 to 2-6 to 1-2 to 1-2. And it has characters of no phosphorus and biodegradability, an environment-friendly water quality stabilizer, used in a water-circulating cooling system to play the role in corrosion inhibition and antifouling.
Description
Technical field
The invention belongs to environmental technology field, be specifically related to a kind of green environment-protective composite slow-corrosion scale resistor that recirculated cooling water is handled that is used for.
Background technology
Though the recirculated cooling water treatment technology is for solving the technology that environmental problem grows up, to water saving, energy-saving and cost-reducing, guarantee the industrial installation safe and stable operation, solve the exhausted problem of global water resources and brought into play crucial effect that but the use of the medicament of circulating water treatment simultaneously also exerts a certain influence to environment.
As far back as phase early 1930s, just begin to adopt inorganic polyphosphate such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, solve the fouling obstruction and the etching problem of water supply system, but scale inhibition and corrosion mitigating effect are not so good, high concentrations of phosphoric acid salt can cause the eutrophication of water body simultaneously.Therefore good chromic salt sour water treatment formulations and the nitrite sour water treatment formulations of corrosion mitigating effect was used widely in 40～fifties of last century; but in view of the carcinogenic harm of chromic salt, nitrate to human body; environment is polluted; along with the increasingly stringent of legislations of environmental protection, the use of this type of medicament is subjected to strict restriction.Middle 1960s organic phospho acid salt inhibiter occurred and has had good scale inhibition and dispersion performance polycarboxylic acid polymkeric substance.Organic phosphoric acid (salt) class Scale inhibitors, polycarboxylic acid Scale inhibitors are compared with inorganic polyphosphate class Scale inhibitors, and they have good chemical stability, not facile hydrolysis, higher water temperature, hardness and the basicity of ability, to CaCO
3Dirt has extremely good restraining effect, and organic phosphonate has reduced the danger that forms calcium phosphate scale because Stability Analysis of Structures and phosphorus content are low simultaneously, has also alleviated the pressure of environment eutrophication.For reducing the discharging of phosphorus, this phosphorus system alkalescence prescription of the recirculated cooling water seventies in 20th century " poly-phosphate-organic phosphonate-polymeric dispersant " has obtained using widely.
Though phosphorus system alkalescence prescription has reduced phosphorus content, its poly-phosphate is still about 15mg/L.The eighties in 20th century, because the increasing of environment protection dynamics, the discharging of phosphorus restriction has become a kind of trend, and phosphine having occurred is all-organic formula " organic phospho acid (salt)-multipolymer ".Phosphine is that phosphonate inhibiter component is generally not high in the all-organic formula, and total phosphorus is about 4mg/L in the recirculated water in service, and corrosive control mainly leans against under the high basicity and moves, and competent OH is arranged in the cathodic area this moment
-, promoted negative electrode to turn usefulness into, provide corrosive environment slowly to steel surface; Ca in alkaline operation in addition
2+And HCO
3 -Generate skim CaCO at steel surface
3Film, the dispersion agent that use properties is good makes CaCO
3Film is very thin, realizes little dirt operation, stops the diffusion of oxygen in water.Phosphine is that all-organic formula is a corrosion inhibitor formula with the organic phosphonate, has reduced phosphorus content, up to the early 1990s this phosphorus be that all-organic formula still accounts for very big proportion.
Late 1980s is to the beginning of the nineties, phosphorous lower inhibiter has appearred, as PBTCA, hydroxyl phosphino-acetate organic phosphine carboxylic acid compounds such as (HPAA), various on the other hand high performance copolymer anti-scale dispersers constantly occur, especially contain multi-functional multipolymers such as sulfonic acid, phosphonic acids, carboxylic acid, because of its good performance causes common concern.Therefore it is good corrosion inhibition to have occurred, " the phosphine carboxylic acid+polymkeric substance " that the scale inhibition dissemination is stronger, the complete organic water treatment prescription all-organic formula of " phosphine carboxylic acid+sulfonic acid polymer " alkalescence.Further reduced phosphorus content, but the phosphine carboxylic acid after all also is the organic water conditioner of phosphorated, though become orthophosphoric acid salt because it is difficult for nature hydrolysis (or decomposition), once be considered to little, be nontoxic the pollution of water body, but because the complicacy of water body itself, organic phosphonate, phosphine carboxylic acid kind difference, hydrolysis (decomposition) time is variant, but can be decomposed into orthophosphoric acid salt eventually and influence water body, cause body eutrophication.
In addition, polycarboxylic acid dirt dispersion agent is as polymkeric substance such as polyacrylic acid, polymaleic anhydride, though once made water technology obtain breakthrough.Since without phosphorus, once be considered to nontoxic, polluted very little, environmentally acceptable water treatment agent.But the water treatment agent lower or nontoxic to these toxicity ignored their long-term accumulated in environment and the potential hazard that causes.Because achievement in research in recent years shows: although most poly carboxylic acid dirt dispersion agent toxicity is lower, but they generally can't resolve into simple nontoxic material under the effect of microorganism and fungi, promptly can't biological degradation or can only be on a small quantity by biological degradation, if in the medium-term and long-term enrichment of water body, also with contaminate environment, especially at some to relatively stricter field of environmental requirement such as offshore oilfield etc.Therefore enter the nineties in 20th century, well-known water treatment enterprises of several families such as the U.S., Japan, Germany all begin to be devoted to seek a kind of energy in succession and substitute poly carboxylic acid, when having good anticorrosion-antiscaling property, biodegradable again " environmental protection " type Water Treatment Chemicals.The exploitation of green corrosion inhibiting and descaling agent poly-epoxy succinic acid of without phosphorus, biodegradable and poly aspartic acid shows that green scale inhibitor has become the direction of water treatment agent development.
The exploitation of external phosphorus-free green water conditioner poly-epoxy succinic acid and poly aspartic acid starts from phase early 1990s.China has also begun synthetic, the scale inhibition of poly-epoxy succinic acid and poly aspartic acid and STUDY ON CORROSION INHIBITION in the later stage nineties.Poly-epoxy succinic acid and poly aspartic acid belong to without phosphorus, have the green water conditioner of good biological degrading activity, and not only the scale inhibition and dispersion performance excellence also has certain corrosion inhibition.
At present, research to poly-epoxy succinic acid and poly aspartic acid mainly is to concentrate on synthetic and scale inhibition both at home and abroad, on the STUDY ON THE DISPERSITY, few to its applied research in recirculated cooling water, poly aspartic acid that has developed in the existing technology and poly-epoxy succinic acid prescription have: and United States Patent (USP) " Method of inhibiting corrosion in aqueoussystems[P] .US5256332; 1993. " a kind of PESA and orthophosphoric acid salt be provided, AA/AHPSE (vinylformic acid/allyl group hydroxypropyl sulfonate ether copolymer), TTA (methylbenzene triazole) forms low-phosphorous prescription, and (15: 3: 5: 3) handle industrial colling, condition of water quality was Ca
2+=400mg/L is (with CaCO
3Meter), Mg
2+=150mg/L is (with CaCO
3Meter), SiO
2=51/L during pH=8.6, is 0.0127mm/a, is 0.00508mm/a. to the corrosion rate of copper the corrosion of Carbon Steel rate.United States Patent (USP) " JudithB.Rockett.Methodforcontrollingscalformationinaqueo ussystems[P] .US5326478; 1994. " provide PESA and TTA (methylbenzene triazole), 2-dodecyl citric acid (Agaricacid) to form without phosphorus prescription (20: 2: 3) processing industrial colling, condition of water quality is Ca
2+=600mg/L is (with CaCO
3Meter), Mg
2+=300mg/L is (with CaCO
3Meter), basicity=400 are (with CaCO
3Meter), Cl
-=425mg/L, SO
4 2-=288mg/L, Na
+49 ℃ of=187mg/L, pH=8.8, water temperatures are 0.00508mm/a to the corrosion of Carbon Steel rate.United States Patent (USP) " WilliamC.Ehrhardt; Longehun Cheng; Dawn Stasney; Kim A.Whitaker.Method and composition forinhibiting corrosion in aqueous systems[P] .US 6585933 B1; 2003. " PESA and AA/AHPSE (vinylformic acid/allyl group hydroxypropyl sulfonate ether copolymer), NBT{3 be provided, 3 '-(3,3 '-dimethoxy-4 ', 4 '-biphenyl)-two-[2-is right-oil of mirbane-two hydrogen-tetrazolium chlorides } and to form without phosphorus prescription (20: 5: 5) and handle industrial colling, condition of water quality is Ca
2+=360mg/L is (with CaCO
3Meter), Mg
2+=180mg/L is (with CaCO
3Meter), Cl
-=255mg/L, SO
4 2-49 ℃ of=220mg/L, pH=300mg, pH=8.6, water temperatures are 0.043mm/a to the corrosion of Carbon Steel rate.United States Patent (USP) " Inhibition of Metal Corrosion.[P] .US 6,277,302B1,2001. " provide PASP and molybdic acid, Zn to form without phosphorus prescription processing industrial colling, condition of water quality is Ca
2+=35mg/L is (with CaCO
3Meter), Mg
2+=25mg/L is (with CaCO
3Meter), basicity=25 are (with CaCO
3Meter), 49 ℃ of pH=8.0, water temperature, be 0.00508mm/a to the corrosion of Carbon Steel rate.
It is few that disclosed poly-epoxy succinic acid, poly aspartic acid are used for recirculated cooling water water treatment compound prescription kind, several examples are only arranged, and the scale-inhibiting properties research to poly-epoxy succinic acid and poly aspartic acid in these patents is more, and to the corrosion inhibition of poly-epoxy succinic acid and poly aspartic acid, especially poly-epoxy succinic acid and poly aspartic acid and other Synergistic Effect of Corrosion Inhibitors research are few, and the inhibition Study of Synergistic Effect between poly-epoxy succinic acid and the poly aspartic acid is not appeared in the newspapers yet.Limited applying of poly-epoxy succinic acid and poly aspartic acid, especially poly-epoxy succinic acid and poly aspartic acid are mutually composite as the recirculated cooling water water conditioner, and have not only appeared in the newspapers as Scale inhibitors but also as the method for inhibiter.Therefore seek to develop the water conditioner that a kind of and poly-epoxy succinic acid and poly aspartic acid have good synergistic effect and will have crucial meaning.
Summary of the invention
Order of the present invention is to provide a kind of without phosphorus, biodegradable green environment-protective composite slow-corrosion scale resistor that recirculated cooling water is handled that is used for.
The green environment-protective composite slow-corrosion scale resistor that is used for the recirculated cooling water processing that the present invention proposes is made up of following component: polyepoxy sodium succinate PESA, poly (sodium aspartate) PASP, hydrolytic polymaleic anhydride HPMA, Sunmorl N 60S GluNa, zinc salt Zn
2+Form.
Among the present invention, polyepoxy sodium succinate: poly (sodium aspartate): hydrolytic polymaleic anhydride: Sunmorl N 60S: zinc salt Zn
2+Mass ratio be 1～6: 1～4: 2～6: 1～2: 1～2.
Among the present invention, polyepoxy sodium succinate: poly (sodium aspartate): hydrolytic polymaleic anhydride: Sunmorl N 60S: zinc salt Zn
2+Mass ratio be 2～5: 1～2: 3～5: 1～2: 1～2.
Among the present invention, described zinc salt Zn
2+For being zinc sulfate, Zn
2+Working concentration be≤4mgL
-1
When independent use polyepoxy sodium succinate PESA, when low consumption, carbon steel is had certain corrosion inhibition, but corrosion inhibition rate is lower.Along with the increase corrosion inhibition of PESA concentration strengthens, consumption is greater than 175mgL
-1The time, can obtain preferably corrosion mitigating effect (Zhang Bingru, Li Hui, Li Fengting. poly-epoxy succinic acid is to the inhibition Study of Synergistic Effect .[J of carbon steel]. Treatment of Industrial Water, 2006,26 (2): 53～56.).When independent use PASP, when low consumption, carbon steel is had certain corrosion inhibition, but corrosion inhibition rate is lower.Along with the increase corrosion inhibition of PASP concentration strengthens, consumption is greater than 250mgL
-1The time, can obtain preferably corrosion mitigating effect (Li Hui, Zhang Bingru, Li Fengting. poly aspartic acid is to the inhibition Study of Synergistic Effect .[J of carbon steel]. water purification technology, 2006,25 (1): 7～10.).
When PESA and PASP are used, exist certain inhibition synergistic effect, than result of use is good separately separately, but it is still bigger, not good enough economically to reach good inhibition efficiency consumption; As PESA and GluNa, PESA and Zn
2+, PASP and HPMA, PASP and GluNa, PASP and Zn
2+All exist certain inhibition synergistic effect when being used in twos, but effect still is not very good, it is still bigger, not good enough economically to reach good inhibition efficiency consumption; And PESA and HPMA non-existent inhibition synergistic effect when being used in twos.
As PESA, PASP, HPMA, GluNa, Zn
2+In any four kinds of components when forming the quaternary compound prescription, all have just short inhibition synergistic effect, can reach good corrosion mitigating effect, and as PESA, PASP, HPMA, GluNa, Zn
2+Form when five yuan of prescriptions are used and then have significant inhibition synergistic effect: work as PESA: PASP: HPMA: Zn
2+Mass ratio 1～6: 1～4: 2～6: 1～2: good corrosion mitigating effect was arranged in 1～2 o'clock; And work as PESA: PASP: HPMA: GluNa: Zn
2+Mass ratio be 2～5: 1～2: better corrosion mitigating effect was arranged in 3～5: 1～2: 1～2 o'clock.
Green environment-protective composite slow-corrosion scale resistor provided by the invention is compared with existing composite slow-corrosion scale resistor has following advantage: (1) this composite slow-corrosion scale resistor belongs to without phosphorus prescription, and the sewage that is discharged in the use can not cause eutrophication pollution to water body.(2) used polymer poly epoxy sodium succinate, poly (sodium aspartate), the hydrolytic polymaleic anhydride of the present invention is the biodegradable product, belongs to environmental friendly product.(3) used polymkeric substance among the present invention, polyepoxy sodium succinate, poly (sodium aspartate), hydrolytic polymaleic anhydride all have good scale inhibition and dispersion performance, can be used in the water quality of high basicity, high rigidity; They also can be used as inhibiter simultaneously in the present invention.(4) the used Sunmorl N 60S of the present invention uses as inhibiter, also belongs to without phosphorus, biodegradable product, and environment is not had detrimentally affect.(5) Zn among the present invention
2+Working concentration be≤4mgL
-1, less than the standard formula of national requirements.(6) have tangible inhibition synergistic effect between the poly-epoxy succinic acid among the present invention, poly aspartic acid, polymaleic anhydride, Sunmorl N 60S, the zine ion, thereby greatly reduce total medicament working concentration.(7) the present invention does not need in addition pre-film before use, and this product can be directly as prefilming agent when high density; Or pre-film need only suitably add in a large number, easy to use when first the use, need not replace medicament, saves use cost.
Embodiment
Further specify the present invention below by embodiment.
Among Comparative Examples of the present invention and the embodiment, the test of corrosion inhibition is with reference to " State Standard of the People's Republic of China GB/T18175-2000, the mensuration one rotary hanging plate method of water conditioner corrosion inhibition ", adopt on the RCC-II type rotary hanging plate corrosion tester and carry out the corrosion inhibition experiment, 45 ℃ of temperature, rotating speed 75r/min, not pre-film lacing film, experimental period 72 hours; Carbon steel test piece: 20
#Carbon steel, 50mm * 25mm * 2mm.
Inhibition experimental water water quality is shown in the table 1:
Table 1: inhibition experiment water quality
| PH | Turbidity | Total hardness mgL -1 | Hardness mgL -1 | Basicity mgL -1 | Total Fe mgL -1 | Cl - mg·L -1 | SO 4 2- mg·L -1 | The total solids solute |
| 7.5 | 0.36 | 138 | 130 | 80 | 0.02 | 79 | 54 | 324 |
Annotate: total hardness, hardness, basicity are all with CaCO
3Meter, mgL
-1
Among Comparative Examples of the present invention and the embodiment, used polyepoxy sodium succinate (hereinafter to be referred as PESA) is the commercially available prod of sea, Jiangsu golden hair exhibition company limited, and its molecular formula is as follows:
Polyepoxy sodium succinate
Used poly (sodium aspartate) (hereinafter to be referred as PASP) is commercially available product, and its molecular formula is as follows:
Poly (sodium aspartate)
Used hydrolytic polymaleic anhydride (hereinafter to be referred as HPMA), Sunmorl N 60S (hereinafter to be referred as GluNa), zinc sulfate are the commercially available prod.
Comparative Examples 1～45
Comparative Examples 1～45th, PESA, PASP, HPMA, GluNa, Zn
2+When being used in twos, mutual inhibition synergistic effect;
Table 2 is that the binary prescription that PESA and PASP form is 50mgL in the medicament total amount
-1The time, to the corrosion inhibition test result of carbon steel.Though therefrom PESA and PASP have certain inhibition synergistic effect (Comparative Examples 2～5) as can be seen, (Comparative Examples 1) corrosion mitigating effect is good during than independent use PASP.When the ratio of PESA surpasses a half, the corrosion mitigating effect good (Comparative Examples 6) during than independent use PESA.But generally speaking corrosion mitigating effect is not very desirable, and consumption is big.
The corrosion inhibition of the binary prescription that table 2 PESA and PASP form
| Comparative Examples | PESA (mg·L -1) | PASP (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 1 | 0 | 100 | 0.8077 | 10.81 |
| Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6 | 20 40 60 80 100 | 80 60 40 20 0 | 0.7929 0.7024 0.3360 0.1461 0.3100 | 12.44 32.32 67.63 85.92 61.64 |
Annotate: the blank assay erosion rate is 0.9056mma
-1
Table 3 is that the binary prescription that PESA and HPMA form is 50mgL in the medicament total amount
-1The time, to the corrosion inhibition test result of carbon steel.As can be seen from the table, when PESA and HPMA are used (Comparative Examples 2～5), when the ratio of PESA during greater than HPMA (Comparative Examples 8, Comparative Examples 9), the corrosion mitigating effect when all using separately good (Comparative Examples 7, Comparative Examples 13) not as PESA, HPMA; When the ratio of PESA is equal to or less than HPMA (Comparative Examples 10～12), though the corrosion mitigating effect when using than PESA is independent is good, but still corrosion mitigating effect is good when using separately not as HPMA.Therefore PESA and HPMA are used the significantly just short inhibition synergistic effect of nothing.
The corrosion inhibition of the binary prescription that table 3 PESA and HPMA form
| Example | PESA (mg·L -1) | HPMA (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 7 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 Comparative Examples 11 Comparative Examples 12 Comparative Examples 13 | 50 40 30 25 20 10 0 | 0 10 20 25 30 40 50 | 0.6880 0.8026 0.7799 0.5880 0.4511 0.4495 0.3482 | 44.56 35.33 37.16 52.62 63.65 63.78 71.94 |
Annotate: the blank assay erosion rate is 1.241mma
-1
Table 4 is that the binary prescription that PASP and HPMA form is 50mgL in the medicament total amount
-1The time, to the corrosion inhibition test result of carbon steel.As can be seen from the table, when PASP and HPMA are used (Comparative Examples 14～19), though the corrosion mitigating effect when using than PASP is independent is good, when PASP: HPMA is 1: 4 (Comparative Examples 18) when using separately than PASP, HPMA corrosion mitigating effect good.Therefore PASP and HPMA are used just short inhibition synergistic effect.
The corrosion inhibition of the binary prescription that table 4 PASP and HPMA form
| Example | PASP (mg·L -1) | HPMA (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 14 Comparative Examples 15 Comparative Examples 16 Comparative Examples 17 Comparative Examples 18 Comparative Examples 19 | 50 40 30 20 10 0 | 0 10 20 30 40 50 | 0.8220 0.8192 0.4843 0.4046 0.2912 0.3482 | 33.76 42.18 60.98 67.40 76.54 71.94 |
Annotate: the blank assay erosion rate is 1.2409mma
-1
Table 5 is that the binary prescription that PESA and Sunmorl N 60S GluNa form is 50mgL in the medicament total amount
-1The time, to the corrosion inhibition test result of carbon steel.As can be seen from the table, PESA and Sunmorl N 60S are used the just short inhibition synergistic effect that (Comparative Examples 21～24) has.
The corrosion inhibition of the binary prescription that table 5 PESA and GluNa form
| Example | PESA (mg·L -1) | GluNa (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 20 Comparative Examples 21 Comparative Examples 22 Comparative Examples 23 Comparative Examples 24 Comparative Examples 25 | 50 40 30 20 10 0 | 0 10 20 30 40 50 | 0.6218 0.6137 0.6540 0.5566 0.6564 0.6803 | 43.39 44.12 40.46 49.33 40.24 38.06 |
Annotate: the blank assay erosion rate is 1.0984mma
-1
Table 6 is that the binary prescription that PASP and Sunmorl N 60S GluNa form is 50mgL in the medicament total amount
-1The time, to the corrosion inhibition test result of carbon steel.As can be seen from the table, when PASP and GluNa are used (Comparative Examples 27～30), significantly just short inhibition synergistic effect is arranged, the corrosion mitigating effect when using separately good (Comparative Examples 26,31) than PASP, GluNa.
The corrosion inhibition of the binary prescription that table 6 PASP and GluNa form
| Example | PASP (mg·L -1) | GluNa (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 26 Comparative Examples 27 Comparative Examples 28 Comparative Examples 29 | 50 40 30 20 | 0 10 20 30 | 0.8685 0.5220 0.5463 0.5585 | 22.63 53.50 51.34 50.25 |
| Comparative Examples 30 Comparative Examples 31 | 10 0 | 40 50 | 0.5021 0.7279 | 55.27 35.16 |
Annotate: the blank assay erosion rate is 1.1226mma
-1
Table 7 is PESA and Zn
2+The binary prescription of forming is 24mgL in the medicament total amount
-1The time to the corrosion inhibition test result of carbon steel.As can be seen from the table, PESA and Zn
2+When being used (Comparative Examples 33～37), significantly just short inhibition synergistic effect is arranged, than PESA, Zn
2+Corrosion mitigating effect good (Comparative Examples 32,38) when using separately.When both are used, has only the Zn of working as
2+Content is greater than 12mgL
-1The time, just can show good corrosion inhibition, but this is much higher than the desired Zn of legislations of environmental protection
2+Quantity discharged≤5mgL
-1Requirement.
Table 7 PESA and Zn
2+The corrosion inhibition of the binary prescription of forming
| Example | PESA (mg·L -1) | Zn 2+ (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 32 Comparative Examples 33 Comparative Examples 34 Comparative Examples 35 Comparative Examples 36 Comparative Examples 37 Comparative Examples 38 | 0 4 8 12 16 20 24 | 24 20 16 12 8 4 0 | 0.8348 0.0395 0.0583 0.0803 0.1666 0.3046 0.7762 | 15.08 95.98 94.06 91.83 83.05 69.02 21.05 |
Annotate: the blank assay erosion rate is 0.9831mma
-1
Table 8 is PASP and Zn
2+The binary prescription of forming is 24mgL in the medicament total amount
-1The time to the corrosion inhibition test result of carbon steel.As can be seen from the table, PASP and Zn
2+When being used (Comparative Examples 40～44), significantly just short inhibition synergistic effect is arranged, than PASP, Zn
2+Corrosion mitigating effect good (Comparative Examples 39,45) when using separately.When both are used, has only the Zn of working as
2+Content is greater than 8mgL
-1The time, just can show good corrosion inhibition, but this is much higher than the desired Zn of legislations of environmental protection
2+Quantity discharged≤5mgL
-1Requirement.
Table 8 PASP and Zn
2+The corrosion inhibition of the binary prescription of forming
| Example | PASP (mg·L -1) | Zn 2+ (mg·L -1) | R (mm·a -1) | η (100％) |
| Comparative Examples 39 Comparative Examples 40 | 24 20 | 0 4 | 1.0125 0.1635 | -0.95 86.82 |
| Comparative Examples 41 Comparative Examples 42 Comparative Examples 43 Comparative Examples 44 Comparative Examples 45 | 16 12 8 4 0 | 8 12 16 20 24 | 0.0293 0.0161 0.0316 0.1384 1.0030 | 97.64 98.70 97.45 88.85 19.18 |
Annotate: the blank assay erosion rate is 1.2410mma
-1
Comparative Examples 46～86
Comparative Examples 46～86th, PESA, PASP, HPMA, GluNa, Zn
2+In the inhibition synergistic effect of the quaternary compound prescription formed of any four kinds of components.
Table 9 is PESA, PASP, HPMA, GluNa, Zn
2+In five kinds of components, the quaternary compound prescription that any four kinds of components are formed be 24mgL in the medicament total amount
-1The time the inhibition synergistic effect.PESA, PASP, HPMA, GluNa, Zn as can be seen from Table 9
2+Be used (Comparative Examples 73～86) Deng any four kinds of components in five kinds of components and all have good inhibition synergistic effect, be better than the corrosion mitigating effect that they are used in twos greatly.
Table 9 also as can be seen the erosion rate of the quaternary compound prescription (Comparative Examples 73～78) formed of PESA, PASP, HPMA, GluNa all greater than 0.2500mma
-1, PESA, PASP, GluNa, Zn
2+The erosion rate of the quaternary compound prescription of forming (Comparative Examples 58～63) is all greater than 0.1000mma
-1, obviously not as PESA, HPMA, GluNa, Zn
2+(Comparative Examples 52～57, erosion rate is less than 0.1000mma
-1) and PASP, HPMA, GluNa, Zn
2+(Comparative Examples 46～51, erosion rate is less than 0.1000mma
-1) and PESA, PASP, HPMA, Zn
2+(Comparative Examples 64～72, erosion rate is less than 0.1000mma for the quaternary compound prescription of forming
-1), it can also be seen that simultaneously the raising of zinc content helps the minimizing of erosion rate (Comparative Examples 79～86).
Table 9 PESA, PASP, HPMA, Zn
2+The corrosion inhibition of the quaternary prescription of forming
| Example | PESA mg·L -1 | PASP mg·L -1 | HPMA mg·L -1 | GluNa mg·L -1 | Zn 2+ mg·L -1 | R mm·a -1 | η 100％ |
| Comparative Examples 46 Comparative Examples 47 Comparative Examples 48 Comparative Examples 49 Comparative Examples 50 Comparative Examples 51 Comparative Examples 52 | 0 0 0 0 0 0 8 | 16 12 8 16 12 8 0 | 4 8 12 2 6 10 12 | 2 2 2 4 4 4 2 | 2 2 2 2 2 2 2 | 0.0629 0.0329 0.0293 0.0496 0.0398 0.0504 0.0484 | 94.24 96.99 97.32 95.47 96.36 97.40 95.58 |
| Comparative Examples 53 Comparative Examples 54 Comparative Examples 55 Comparative Examples 56 Comparative Examples 57 Comparative Examples 58 Comparative Examples 59 Comparative Examples 60 Comparative Examples 61 Comparative Examples 62 Comparative Examples 63 Comparative Examples 64 Comparative Examples 65 Comparative Examples 66 Comparative Examples 67 Comparative Examples 68 Comparative Examples 69 Comparative Examples 70 Comparative Examples 71 Comparative Examples 72 Comparative Examples 73 Comparative Examples 74 Comparative Examples 75 Comparative Examples 76 Comparative Examples 77 Comparative Examples 78 Comparative Examples 79 Comparative Examples 80 Comparative Examples 81 Comparative Examples 82 Comparative Examples 83 | 12 16 16 12 8 16 12 8 16 12 8 4 8 12 16 4 8 12 8 4 12 8 4 12 8 4 0 0 16 16 8 | 0 0 0 0 0 4 8 12 2 6 10 16 12 8 4 12 8 4 4 8 4 8 12 4 8 12 8 16 0 0 12 | 8 4 2 6 10 0 0 0 0 0 0 2 2 2 2 6 6 6 10 10 4 4 4 6 6 6 12 2 4 2 0 | 2 2 4 4 4 2 2 2 4 4 4 0 0 0 0 0 0 0 0 0 4 4 4 2 2 2 2 4 2 4 2 | 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 0 0 0 0 0 0 4 4 4 4 4 | 0.0266 0.0456 0.0362 0.0248 0.0359 0.1211 0.1533 0.1874 0.1041 0.1527 0.2034 0.0982 0.0835 0.0436 0.0394 0.0759 0.0459 0.0393 0.0269 0.0341 0.2501 0.2892 0.3033 0.2303 0.2741 0.2934 0.0195 0.0358 0.0298 0.0237 0.0689 | 97.57 95.83 96.54 97.63 96.57 88.45 85.38 82.12 90.07 85.43 80.60 91.36 92.64 96.16 96.53 93.32 95.96 96.54 98.19 97.00 80.17 77.06 75.95 81.74 78.27 76.74 98.21 96.72 97.27 97.83 93.70 |
| Comparative Examples 84 Comparative Examples 85 Comparative Examples 86 | 16 16 4 | 2 4 12 | 0 2 6 | 4 0 0 | 4 4 4 | 0.0653 0.0283 0.0538 | 94.02 97.41 95.08 |
Annotate: the blank assay erosion rate of Comparative Examples 46～54 is 1.0938mma
-1The blank assay erosion rate of Comparative Examples 55～63 is 1.0486mma
-1
The blank assay erosion rate of Comparative Examples 64～72 is 1.1360mma
-1The blank assay erosion rate of Comparative Examples 73～78 is 1.2612mma
-1
The blank assay erosion rate of Comparative Examples 79～86 is 1.0936mma
-1
Embodiment 1～16
Table 10 is PESA, PASP, HPMA, GluNa, Zn
2+The inhibition synergistic effect of five yuan of compound prescriptions forming Deng five kinds of components, PESA, PASP, HPMA, GluNa, Zn as can be seen
2+Be used Deng five kinds of components, there is good inhibition synergistic effect, obviously be better than the binary compound prescription (Comparative Examples 1～45) that any two components are formed in them, also be better than the corrosion mitigating effect (Comparative Examples 46～86) of the quaternary compound prescription that any four components are formed in them.
Table 10 PESA, PASP, HPMA, GluNa, Zn
2+The corrosion inhibition of five yuan of prescriptions forming
| Example | PESA mg·L -1 | PASP mg·L -1 | HPMA mg·L -1 | GluNa mg·L -1 | Zn 2+ mg·L -1 | R mm·a -1 | η 100％ |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 | 6 8 12 10 8 4 6 4 2 8 8 4 4 8 | 8 6 4 2 4 8 2 4 6 4 2 6 4 4 | 6 6 4 8 8 8 12 12 12 6 8 8 10 4 | 2 2 2 2 2 2 2 2 2 2 2 2 2 4 | 2 2 2 2 2 2 2 2 2 4 4 4 4 4 | 0.0072 0.0055 0.0022 0.0018 0.0000 0.0061 0.0056 0.0082 0.0058 0.0096 0.0011 0.0059 0.0043 0.0048 | 99.42 99.55 99.82 99.85 100.00 99.49 99.55 99.33 99.49 99.22 99.85 99.49 99.62 99.63 |
| Embodiment 15 embodiment 16 | 4 4 | 4 8 | 8 6 | 4 4 | 4 4 | 0.0042 0.0083 | 99.46 99.28 |
Annotate: the blank assay erosion rate of embodiment 1～9 is 1.2310mma
-1The blank assay erosion rate of embodiment 10～16 is 1.1486mma
-1
Embodiment 1～16 explanation PESA, PASP, HPMA, GluNa, Zn
2+Exist significant inhibition synergistic effect between five, and PESA: PASP: HPMA: GluNa: Zn
2+Mass ratio be 1～6: 1～4: best corrosion mitigating effect was arranged in 2～6: 1～2: 1～2 o'clock, and its erosion rate is less than 0.0100mma
-1And work as PESA: PASP: HPMA: GluNa: Zn
2+Mass ratio be 2～5: 1～2: better corrosion mitigating effect is arranged at 3～5: 1～2: 1～2 o'clock, its erosion rate is less than 0.0050mma
-1, corrode the higher limit 0.125mma that allows far below " Code for design of industrial recirculating cooling water treatment " medium carbon steel
-1Therefore the compound prescription among the present invention has higher corrosion mitigating effect, and without phosphorus, biodegradable, belongs to the environmental type prescription of environmentally safe, thereby has wide market application prospect.
Claims (4)
1, a kind of green environment-protective composite slow-corrosion scale resistor that is used for the recirculated cooling water processing is characterized in that being made up of following component: polyepoxy sodium succinate, poly (sodium aspartate), hydrolytic polymaleic anhydride, Sunmorl N 60S, zinc salt Zn
2+Form.
2, the green environment-protective composite slow-corrosion scale resistor that is used for the recirculated cooling water processing according to claim 1 is characterized in that polyepoxy sodium succinate: poly (sodium aspartate): hydrolytic polymaleic anhydride: Sunmorl N 60S: zinc salt Zn
2+Mass ratio be 1～6: 1～4: 2～6: 1～2: 1～2.
3, the green environment-protective composite slow-corrosion scale resistor that is used for the recirculated cooling water processing according to claim 1 is characterized in that polyepoxy sodium succinate: poly (sodium aspartate): hydrolytic polymaleic anhydride: Sunmorl N 60S: zinc salt Zn
2+Mass ratio be 2～5: 1～2: 3～5: 1～2: 1～2.
4, the green environment-protective composite slow-corrosion scale resistor that is used for the recirculated cooling water processing according to claim 1 is characterized in that described zinc salt Zn
2+Be zinc sulfate.
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