CN1020200C - Corrosion inhibitor of cooled water in closed cycle - Google Patents
Corrosion inhibitor of cooled water in closed cycle Download PDFInfo
- Publication number
- CN1020200C CN1020200C CN 89106699 CN89106699A CN1020200C CN 1020200 C CN1020200 C CN 1020200C CN 89106699 CN89106699 CN 89106699 CN 89106699 A CN89106699 A CN 89106699A CN 1020200 C CN1020200 C CN 1020200C
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- China
- Prior art keywords
- water
- corrosion
- corrosion inhibitor
- inhibitor
- benzotriazole
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a corrosion inhibitor for cooling water treatment in a closed cycle, particularly to a silicon system inhibitor. The corrosion inhibitor has a prescription of the compound corrosion inhibitor that sodium silicate used as main agents is matched with hydroxy ethylidene phosphonic acid, sodium gluconate and benzotriazole. The inhibitor has the advantages of high efficiency, no toxicity, stabilisation, low cost and easy operation, is suitable for high-water temperature systems without deoxidization for softening water or removing salt water; the present invention has the performance of chlorine ion corrosion resistance, and has no deposition on wall surfaces, without prefilming treatment to the systems in use.
Description
The present invention relates to a kind of corrosion inhibition method that is used for inclosed recirculated cooling water.
In process water, the water consumption of water coolant accounts for significant proportion.Generally the dissolved impurity of its water coolant and suspended impurity can form incrustation scale or corrosion at the heating surface of equipment in the process of using open-type cooling water, cause equipment, pipeline damage and productivity is descended, directly influence economic benefit, therefore must handle to slow down its fouling and corrosive nature water coolant.Recently the inclosed recirculated cooling water system that grows up is to be heat-eliminating medium with softening water (or de-mineralized water), though relaxed scale problems like this, has brought serious system's etching problem.When adopting the inclosed recirculated cooling water system, must carry out inhibition to soft water and handle for this reason.
The inhibiter that has now used has multiple, and phosphorus line formulation commonly used is because host is poly-phosphate, so at scarce Ca
2+Water in (as being lower than 10ppm), with regard to restive corrosion, the speed that poly-phosphate is hydrolyzed into positive phosphorus when the higher and heat conductive wall temperature of water temperature is higher is accelerated, thereby loses efficacy, water coolant pH is too high also should not to use poly-phosphate, should not adopt phosphorus line formulation in inclosed recirculated cooling water is handled for this reason.Though the good expense of corrosion mitigating effect of chromium system prescription is also low, its toxicity is big, if mismanagement just pollutes the environment, and all few both at home and abroad now using.Organic phosphonate is more stable than poly-phosphate, and it is an effective corrosion inhibitors prescription that organic phosphonate and zinc salt are used, but Zn
2+Be higher than at 7.5 o'clock at pH, easily deposition so not only loses corrosion inhibiting ability, and influences the heat transfer efficiency of cooling-part, therefore as using this class inhibiter just to need to regulate the pH value.Cause the complicacy of equipment and operation.So got rid of this type of corrosion inhibitor formula in this system.The nitrite of the effective inhibiter that uses as the inclosed recirculated cooling water system, its application also has very long history, prevents that it is oxidized to nitrate and the sterilant that lost efficacy but should cooperate to add, otherwise the reagent consumption amount.Especially in the last few years found its nitrosamine problem, so the oxidation deactivation of nitrite and carcinogenesis thereof have influenced the application of this type of medicament.Domestic imitation is from E100 number of the Germany introduction, and promptly the PTX-CS inhibiter also is a kind of effective inhibiter that is used for airtight treatment of cooling water, but general throwing amount is big, costs an arm and a leg.Molybdenum system prescription is a kind of effective anodic corrosion inhibitor, and toxicity is less, but promotes the use of because of the higher inconvenience of molybdate price.
Existing silicon is that neutralization technology only sees that being used for the open type recirculated cooling water handles and the semi closed circulating water system.Its prescription of Si series corrosion inhibitor that has obtained patent as U.S. Betz company is water glass 10ppm, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 10ppm, carboxymethyl cellulose 20ppm, benzotriazole 3ppm, pH is 8.5 during use, non-softening water, with Sodium hexametaphosphate 99 and the pre-film of zinc sulfate 800ppm, this Si series corrosion inhibitor prescription only is applicable to the open type recirculating cooling water system.Other has the semi closed circulating water system (to refer to that system has ventpipe to lead to atmosphere, oxygen in water descends in a large number when the operation water temperature rises) employed Si series corrosion inhibitor, its condition is that water coolant is handled without softening from surface water, add water glass 2000～5000ppm, though can control corrosion of carbon steel, have incrustation scale to generate.
The silicon that the objective of the invention is efficient by developing, nontoxic, as to stablize, be applicable to not deoxidation inclosed recirculated cooling water inhibition is the compound slow corrosion agent prescription, and utilize the proportioning of this prescription, the compatibility medicament is added in water, be applicable to not deoxidation with establishment, adjust pH not, the corrosion inhibition method of the easy handling of the inclosed recirculated cooling water that water temperature is high.
In order to achieve the above object, the present invention takes following measures: through the static formulation screening test of testing laboratory, thereby this corrosion inhibition method is established in dynamic analog test and production scene commerical test, and the inhibiter that this method is used is with water glass, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Sunmorl N 60S (C
6H
11O
7Na) and benzotriazole (BTA) compatibility.When water glass with silicon-dioxide (SiO
2) meter, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) is with phosphate radical (PO
3- 4) meter, all the other are with this industrial goods weight timing, the adding than being SiO of each compatibility medicament
2: PO
3- 4: C
6H
11O
7Na: BTA=1500～3000: 20～50: 200～400: 1～3.During the modulation inhibiter, water glass can be dissolved in softening water, successively with 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Sunmorl N 60S (C
6H
11O
7Na) and benzotriazole (BTA) add in the entry.A kind of medicament of every adding all should stir.Finally be made into 10% solution.These all carry out at normal temperatures and pressures, and only benzotriazole (BTA) will be dissolved in a small amount of alcohol earlier, adds water then.
In the inclosed recirculated cooling water processing commerical test of No. three blast furnaces of Taiyuan Iron ﹠ Steel Corp, utilize this corrosion inhibition method to handle sealing and circulating soft water, need not adjust water coolant pH, also without deoxidation, its corrosion rate is under the target value 0.047mm/y of the similar inclosed recirculated cooling water treatment system regulation of Chinese Baoshan Iron and Steel Company head factory in Castanea crenata field company, i.e. 0.0003～0.023mm/y, and on average adhere to speed is 0.0027～0.227mcm, does not find in trial period that the developmental tube heat transfer efficiency descends.When containing the distilled water of chlorion, as Cl with this corrosion inhibition method processing
-≤ 2000ppm does not have obvious influence to the corrosion of carbon steel rate, can anti-chlorine ion corrosion.This corrosion inhibition method also is applicable to the inhibition processing of de-mineralized water except being applicable to soft water, and the high system of water temperature, does not need that in use system is made pre-film and handles.
Below further describe for example:
This example is that the inclosed recirculated cooling water system water of No. three blast furnaces of Taiyuan Iron ﹠ Steel Corp is handled commerical test.
Sealing and circulating water flow to air-cooler through built on stilts DN300 pipeline after blast furnace cooling stave is discharged, water coolant is delivered to blast furnace cooling stave again by the water circulating pump pressurization and used after the air-cooler cooling.On the arm between air-cooler and the water circulating pump, be connected to the expansion narrow-necked earthen jar.On the arm between water circulating pump and the blast furnace, be provided with high-order safe water tank.The required water treatment agent of recirculated cooling water injects on water pump suction pipe.
The main design parameters of system is as follows:
Quantity of circulating water 450m
3/ h
50～55 ℃ of feed temperatures
60～65 ℃ of return water temperatures
Operating pressure 0.7MPa
System volume～70m
3
The water quality of pilot system
Total hardness 0.005mg/L, total alkalinity 1.3mg-N/L, Cl
-18mg/L, SO
2- 438.68mg/L, SiO
24.8mg/L, Na
+67mg/L, total dissolved solidss 148.11mg/L, burning decrement 26mg/L, Ca
2+Trace, Mg
2+Trace, K
+Trace, pH9.95, specific conductivity 160 μ s/cm.
The corrosion inhibition method that present embodiment uses, inhibiter component and throwing amount are: water glass (SiO
2Meter): HEDP(PO
3- 4Meter): Sunmorl N 60S (industrial goods meter): benzotriazole (industrial goods meter)=1000～2000ppm: 30ppm: 400ppm: 1ppm.
The monitoring of water treatment effect, carry out in the following manner:
The water temperature record feeds water by circulation and understands the transmission heat of recirculated water, the i.e. heat-transfer effect of cooling component with the backwater water temperature.Table 1 is average feedwater and the backwater water temperature by ten days from February 29, in 87 on October 1, to 88.
Lacing film is analyzed: by weightening finish, the weightlessness of weighing lacing film, can calculate and adhere to speed m.c.m value and corrosion rate.
Table 2(table 2a, 2b) be all previous lacing film adhere to speed m.c.m and corrosion rate.
Taiyuan Iron and Steel Co. three blast furnace inclosed recirculated cooling water test run water temperature data statistics 1
Water temperature (℃) rate of water make-up (L)
Date
Average day of the import export temperature difference
In October, 1987
1-10 47.06 50.73 3.67
11-20 51.93 55.98 4.05 559
21-31 53.33 56.09 2.76
In November, 1987
1-10 51.28 54.35 3.08
11-20 53.55 56.31 2.76 235
21-30 51.56 54.60 3.04
In December, 1987
1-10 47.15 51.69 4.54
11-20 51.05 55.30 4.25 359
21-31 52.57 54.85 2.28
In January, 1988
1-10 51.61 52.94 1.33
11-20 52.73 54.86 2.14 92
21-31 46.22 49.15 2.94
In February, 1988
1-10 51.36 54.77 3.41
11-20 48.92 52.65 3.73 81
21-29 50.93 54.73 3.80
Production scene lacing film monitoring result table 2a
Preface lacing film position lacing film time lacing film weight (g)
Number and after the lacing film original weight cleans before cleaning
87.10.17-11.5
1 pump preceding 20.0617 20.0657 20.0355
454 hours
87.11.5-12.8
2 pumps preceding 19.9203 19.9197 19.9175
794 hours
87.11.5-12.8
3 backwater 20.0127 20.0123 20.0097
794 hours
87.12.8-12.24
4 backwater 18.8848 18.8812 18.8769
388 hours
87.12.8-12.24
5 pumps preceding 20.4008 20.3937 20.3875
388 hours
87.12.24-88.3.12 before the pump
6 19.7659 19.7622 19.7606
1,049 1896 hours
Backwater 87.12.24-88.3.12
7 19.7432 19.7422 19.7381
1,050 1896 hours
88.3.12-5.20 before the pump
8 19.6531 19.6539 19.6518
1,046 1674 hours
Backwater 88.3.12-5.20
9 19.6749 19.6751 19.6736
1,047 1674 hours
Backwater 88.5.20-7.18
10 19.7236 19.7210 19.7161
1,041 1416 hours
88.5.20-7.18 before the pump
11 19.2895 19.2910 19.2847
1,048 1416 hours
Production scene lacing film monitoring result table 2b
The weightless weightening finish of preface corrosion rate adheres to speed
Outward appearance is described
Number (g) be (mm/y) m.c.m. (g)
1 0.0262 0.0040 0.023 0.227
2 0.0028-0.0006 0.0014-0.019 no rust spots, the two sides is glossy.
3 0.0030-0.0004 0.0015-0.013 no rust spots, the two sides is glossy.
4 0.0079-0.0036 0.0081-0.239 one sides have golden colour lustre, and one side has tinge.
5 0.0133-0.0071 0.0137-0.471 one sides have dark yellow, face portion blackout, no rust spot, hot spot.
6 0.0053-0.0037 0.0011-0.050 is rustless, shinny, scratches vestige.
7 0.0051-0.0010 0.0011-0.014 is rustless shinny, scratches vestige.
There is white point at 8 0.0013 0.0008 0.0003 0.012 one edges, and there is black flower sheet in big portion, and the shinny gloss of one side has cut.
9 0.0013 0.0002 0.0003 0.003 one sides have half spot that is white in color, precipitation that the chances are, and one side has a small amount of white point.
10 0.0075-0.0026 0.0021-0.0047 two sides non-corrodings do not have vestige, shinny gloss.
11 0.0048 0.0015 0.0014 0.0027 is the same
Annotate: table 2b is the continuous table of 2a.
The mean value of 11 data of corrosion rate is 0.0049mm/y.
Water treatment effect: as can be seen from Table 2, the result of all previous lacing film monitoring shows, utilizing corrosion inhibition method of the present invention to carry out inhibition, to handle annual corrosion rate be 0.003～0.023mm/y, compares all up to standardly with target value 0.047mm/y, and the circulation soft water corrosion rate that does not deal with is 2.16mm/y.
Adhering to speed most of is negative value, and on the occasion of being 0.0027～0.227m.c.m, illustrating does not have dirt settling substantially in the test piece.
From these data, the water treatment effect is gratifying.
About the water temperature problem:, and do not reached the numerical value of system design in the water temperature and the temperature difference of run duration.Is 53.55 ℃ by the highest water inlet water temperature of the mean of dekan from October, 1987～1988 between year February, and maximum water temperature is 56.31 ℃, and maximum temperature difference is 4.54 ℃.Table 1 is remembered the water temperature situation, and irregular saying, does not see temperature difference decline trend.This phenomenon should be merely from water system, and the working of a furnace that more influence factor should be blast furnace changes.When the working of a furnace can not remain unchanged, water temperature was not seen regular.
According to the cooling-part thermic load, soft water, the inclosed recirculated cooling water that service condition etc. utilize corrosion inhibition method of the present invention to carry out is processed income effect, and the method is applicable to the smelting equipment that thermic load is high, the inclosed recirculated cooling water inhibition of soft water or demineralized water. The corrosion inhibitor formula that method is used has efficiently, and good stability is pollution-free, adjust pH not, and the high chlorine resistant root, inexpensive, the advantages such as easy operating. But in conjunction with closed system extension device life-span still, save water and energy. Can promote the use of fully.
Claims (1)
1, a kind of corrosion inhibition method that is used for inclosed recirculated cooling water is characterized in that adding by water glass in this water coolant, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Sunmorl N 60S (C
6H
11O
7Na) and the composite corrosion inhibitor formed of benzotriazole (BTA), weight (ppm) proportioning of each component of this inhibiter in water coolant is that [water glass is with silicon-dioxide (SiO
2Meter, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is with phosphate radical (PO
4 3-Meter, Sunmorl N 60S and benzotriazole are in this industrial goods weight]:
SiO
2∶PO
4 3-∶C
6H
11O
7Na∶BTA=1500～3000∶20～50∶200～400∶1～3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106699 CN1020200C (en) | 1989-09-05 | 1989-09-05 | Corrosion inhibitor of cooled water in closed cycle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106699 CN1020200C (en) | 1989-09-05 | 1989-09-05 | Corrosion inhibitor of cooled water in closed cycle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050053A CN1050053A (en) | 1991-03-20 |
| CN1020200C true CN1020200C (en) | 1993-03-31 |
Family
ID=4856838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106699 Expired - Fee Related CN1020200C (en) | 1989-09-05 | 1989-09-05 | Corrosion inhibitor of cooled water in closed cycle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020200C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052763C (en) * | 1995-11-15 | 2000-05-24 | 首钢总公司 | Si Series corrosion inhibitor for soft water close circulation cooling system |
| CN1063803C (en) * | 1997-11-28 | 2001-03-28 | 中国石油化工总公司 | Composite corrosion-inhibiting antisludging agent for strong corrosive water |
| CN100424228C (en) * | 2006-01-14 | 2008-10-08 | 中国海洋大学 | Scale and corrosion inhibitor for inhibiting corrosion of carbon steel |
| CN102452724B (en) * | 2010-10-20 | 2014-01-29 | 中国石油化工股份有限公司 | Composite corrosion and scale inhibitor and its application in water treatment |
| CN107892398A (en) * | 2017-12-11 | 2018-04-10 | 唐山金沙水处理有限公司 | Recirculated water closed system corrosion inhibiter and its preparation and application method |
| CN111673930B (en) * | 2020-05-15 | 2022-03-15 | 电子科技大学 | Electronic material cutting cold working fixed condensate and device |
| CN113322466B (en) * | 2021-06-28 | 2023-04-28 | 西安热工研究院有限公司 | Corrosion inhibitor applied to SCAL indirect air cooling system and dosing method thereof |
-
1989
- 1989-09-05 CN CN 89106699 patent/CN1020200C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1050053A (en) | 1991-03-20 |
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