CN1189731C - Method for evaluating the affection of water treatment agent to corrosion-resistance of stainless steel - Google Patents
Method for evaluating the affection of water treatment agent to corrosion-resistance of stainless steel Download PDFInfo
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- CN1189731C CN1189731C CN 03115664 CN03115664A CN1189731C CN 1189731 C CN1189731 C CN 1189731C CN 03115664 CN03115664 CN 03115664 CN 03115664 A CN03115664 A CN 03115664A CN 1189731 C CN1189731 C CN 1189731C
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Abstract
The present invention relates to a method for evaluating the influence of a cooling water treatment agent to the corrosion resisting properties of stainless steel. The difference of the pitting potentials of the stainless steel in a blank sample and a non-empty water sample indicates the influence of the water treatment agent on the corrosion resisting properties of the stainless steel, the pitting potential of the measured stainless steel in at least one blank water sample is within the range of 300 to 900mV, and the range is preferably from 400 mV to 600 mV. The present invention can largely improve the resolution, the reliability and the integrity of evaluating the influence of the water treatment agent on the corrosion resisting properties of the stainless steel, and prevent erroneous judgment and missed judgment.
Description
Technical field
The present invention relates to a kind of method of evaluating water treatment agent to the influence of metal material corrosion resisting property.
Background technology
In short supply day by day along with water resource, for using water wisely, reasonable use of water, the concentration rate of recirculated cooling water improves constantly.The contradiction of fouling, burn into biohazard becomes increasingly conspicuous.The application of various water treatment agents in chilled water is more and more, and stainless steel also is used for the heat transfer element of cooling water system heat interchanger, the particularly cooling tube of thermal power plant's condenser more and more.The U.S. has 70% condenser employing stainless-steel tube approximately, and China uses the power plant of stainless steel pipe condenser also increasing sharply.The water treatment agent that has has corrosion inhibition to metal material, and what have has a corrosion facilitation, the not influence that also has.For the normal safe operation of assurance equipment, must evaluate the influence of water treatment agent to the metal material corrosion resisting property.
The method that prior art adopts the corrosion weight loss method to measure the corrosion speed of metal material in chilled water is usually estimated the influence of cooling water treatment agent to the metal material corrosion resisting property.Document [1] " GB50050-95 industrial circulating water Treatment Design standard " requires the rate of corrosion of the recirculated cooling water side pipe wall of heat transmission equipment, when no technological requirement, should meet the following requirements: " corrosion speed of carbon steel tube wall should be less than 0.125mm/a, the corrosion speed of copper, aldary and stainless steel tube wall should less than 0.005mm/a ".The method of testing of this corrosion speed generally all adopts the corrosion weight loss method, and document [2] " the mensuration rotary hanging plate method of HG/T2159-91 water treatment agent corrosion inhibition " has stipulated to measure with the rotary hanging plate corrosion weight loss method of corrosion speed.Carbon steel is the common used material of cooling water system heat interchanger; with corrosion weight loss method evaluation water treatment agent the influence of carbon steel corrosion resisting property there are rationality and reliability preferably; because carbon steel can have than obvious corrosion weightlessness in the short time in chilled water usually, and common corrosion failure form is a uniform corrosion.Water treatment agent to the influence of stainless steel corrosion resisting property then study few, many people still continue to use traditional weight-loss method, " lijin etc.; generating plant circulation-water water quality stabilizer scale inhibition and the research of corrosion inhibition envelope test; North China power technology; 1998, (10): 18 " have just adopted this method as document [3], but the mutual contradiction of corrosion weight loss experimental data.Wherein the corrosion resisting property of the one group of Notes of Key Data 316 stainless steel in chilled water is significantly less than 304 stainless steels, and this and everybody admitted facts are not inconsistent.We also consulted the test report of some units, and inquired into testing crew, generally believed that the corrosion weight loss of stainless steel in chilled water is too little, were difficult to record standard.We also once differed at erosion performance and did the corrosion weight loss test in the great chilled water, and in year, corrosion weight loss is all almost nil in tens of skies; Also once with 304,316L, 317L stainless-steel tube be immersed in the saliva of the Changjiang river 1 year, corrosion weight loss still is almost nil, can not distinguish the height of the stainless steel corrosion resisting property of the different trades mark; Also once added different water treatment agents in same chilled water, stainless steel has soaked hundreds of hours therein, and corrosion weight loss is also all almost nil, can not distinguish the corrosion influence of these medicaments, and table 2 is partial datas of this test.We think that this is not fortuitous phenomena, because the corrosion weight loss amount of stainless steel in chilled water is minimum, and clean, sum of the deviations that processes such as drying and weighing are brought is probably greater than the corrosion weight loss amount, therefore be easy to get the wrong sow by the ear or can not differentiate the corrosion influence degree.In addition, the main corrosion failure form of stainless steel in chilled water is local corrosion, and be also unreasonable with weight-loss method.
With their pitting resistance of height evaluation of stainless steel pitting potential in same water quality of the different trades mark, perhaps use and just evaluate these water quality with the pitting potential of a kind of stainless steel in different quality and obtained in the prior art generally acknowledging in the aggressivity aspect the spot corrosion.Clearly do not stipulate under what conditions but see prior art such as the present invention as yet, evaluate of the influence of chilled water water treatment agent the stainless steel corrosion resisting property with the height of pitting potential.If main corrosion failure form is stress corrosion, then evaluating the chilled water water treatment agent with the height of pitting potential is skimble-skamble to the influence of stainless steel corrosion resisting property.Document [3] has also adopted the pitting resistance of height evaluation stainless steel in containing the water sample of these water quality stabilizers with pitting potential, but do not spell out this place's pitting resistance and whether just can represent corrosion resisting property, be not benchmark also, more the scope of the pitting potential in the blank water sample do not made clearly regulation with the pitting potential in the blank water sample.
Summary of the invention
The purpose of this invention is to provide a kind of easier, resolution and reliability again than the method for higher evaluation chilled water water treatment agent to the influence of stainless steel corrosion resisting property.
The cooling water treatment agent that the present invention proposes is to the assessment method of stainless steel corrosion resisting property influence, is with the chilled water water treatment agent influence of pitting resistance of stainless steel to be characterized the influence of water treatment agent to the stainless steel corrosion resisting property.
The corrosion failure form of the stainless steel heat transmission equipment in the cooling water system has spot corrosion, crevice corrosion, intercrystalline corrosion, stress corrosion and biological corrosion etc.If the stainless steel workmanship is out of question, welding technology is correct during device fabrication, and the quality management strictness then generally intercrystalline corrosion can not take place.If clean or add the cleaning (keep clean also is to guarantee the normal needs that conduct heat) of effective antisludging agent, spreading agent and biocide maintenance stainless steel heat transfer element by machinery, then generally also crevice corrosion and biological corrosion can not take place, and the ability of stainless slit and corrosion resistant ability and anti-spot corrosion is closely-related.Although the inefficacy form that stainless steel is maximum is stress corrosion, when water sidewall temperature is less than a certain temperature value during as if operate as normal, then generally stress corrosion can not take place.This temperature generally can be defined as about 65 ℃.Condenser just belongs to this situation.Therefore in condenser and other cooling water system under regular service condition the dividing wall type heat exchanger stainless steel heat transfer element of cooling water side wall temperature＜65 ℃ (as the cooling tube in the tubular heat exchanger, heat transfer plate in the plate type heat exchanger or the like), spot corrosion should be main corrosion failure form, therefore, the present invention selects for use pitting resistance to represent its corrosion resisting property.
Measure the pitting potential of stainless steel in the water sample that does not contain the water treatment agent that to evaluate (abbreviating blank water sample as).Blank water sample kind 〉=1, and have a kind of blank water sample at least, tested stainless steel pitting potential therein in 300～900mV scope, preferred 580 ± 100mV (current potential of the present invention is all with respect to saturated calomel electrode SCE).If pitting potential not in above-mentioned scope, then can adopt non-evaluation of adjusting in the water sample to become to grade method,, make its pitting potential within the limits prescribed as increase and decrease chlorine ion concentration and/or sulfate ion concentration.Blank water sample can preferentially be selected actual chilled water preparation for use with the also available pure water of actual chilled water (as deionized water) preparation.
A large amount of experimental studies through the inventor prove, same water treatment agent agent influence to same stainless steel pitting potential in different blank water samples is different, different in other words blank water samples have different resolution, stainless pitting potential is in 300～900mV scope the time, the chilled water composition is changed relatively sensitivity, and susceptibility is higher in the 580mV left and right sides.When stainless pitting potential during less than 300mV, not only the susceptibility that the chilled water composition is changed reduces, and does not meet the requirement to the stainless steel corrosion resisting property, and this is the stainless steel selection and uses institute unallowed, also is rarely found therefore.Certain situation is arranged, and the pitting potential of stainless steel in chilled water be greater than 900mV, and this moment, stainless pitting potential was also very low to the susceptibility that the chilled water composition changes, and judges by accident and the possibility of failing to judge increases greatly.Therefore, we are when using the pitting potential method to estimate water treatment agent to the influencing of stainless steel corrosion resisting property, not only to do blank water sample with actual water sample, whether be also noted that needs to change a little blank water sample condition, improve the resolution of test water sample, have a kind of blank water sample at least, tested stainless steel pitting potential therein is in 300～900mV scope, preferred 580 ± 100mV prevents to judge by accident and fail to judge.
In above-mentioned blank water sample, add the water treatment agent that to evaluate of normal concentration, make the non-blank-white water sample.With measure the pitting potential of stainless steel in the non-blank-white water sample that to evaluate with quadrat method.
The pitting potential of stainless steel in non-blank-white water sample and blank water sample relatively is if the pitting potential Ea of the pitting potential Eb of stainless steel in the non-blank-white water sample＞in blank water sample judges that then this water treatment agent has corrosion inhibition to this stainless steel under this concentration; If the pitting potential Ea of the pitting potential Eb of stainless steel in the non-blank-white water sample＜in blank water sample judges that then this water treatment agent has the corrosion facilitation to this stainless steel under this concentration; If these two kinds of pitting potentials do not have significant difference, judge that then this water treatment agent does not make significant difference to this Corrosion Resistance of Stainless Steels under this concentration.If water treatment agent has different influences in different blank water samples, then be as the criterion with the blank water sample preferred, that resolution is higher, perhaps illustrate in which kind of water sample, to have which kind of influence respectively.Generally, the pitting potential of tested stainless steel in blank water sample is 300-900mV.
The invention has the beneficial effects as follows and improved resolution, reliability and the integrality of evaluation water treatment agent greatly, prevent to judge by accident and fail to judge the influence of stainless steel corrosion resisting property.
Embodiment
Below in conjunction with the specific embodiment explanation specific embodiment of the invention.Yet, mandatory declaration be that the present invention is not limited to these specific embodiments.
1, three kind of anti-incrustation corrosion inhibitor of embodiment in the Q circulating cooling water of power plant to the evaluation of stainless steel pipe condenser corrosion mitigating effect.
Q power plant two 350MW unit condensers cooling tube all is 304 stainless-steel tubes, and the concentration rate of recirculated cooling water is about 2.This factory prepares to carry out waste water zero emission, and concentration rate is brought up to more than 4, requires evaluation three kinds of anti-incrustation corrosion inhibitor a, b and the c corrosion mitigating effect to stainless steel pipe condenser in this factory's recirculated cooling water.Estimation steps is as follows:
1, with anti-incrustation corrosion inhibitor the influence of pitting resistance of stainless steel is evaluated this medicament to stainless corrosion mitigating effect.
2, select two kinds of blank water samples, the one, actual cycle chilled water (concentration when pressing concentration rate 4, Cl that this factory provides
-36mg/L, SO
4 2-44mg/L is not with water treatment agent); The 2nd, in the actual cycle chilled water that this factory provides, add NaCl and Na
2SO
4, make Cl
-And SO
4 2-Be 200mg/L.Measure the pitting potential of 304 stainless steels in blank water sample, measurement result sees Table 1.
3, in above-mentioned blank water sample, add anti-incrustation corrosion inhibitor a, b and the c of normal concentration, make the non-blank-white water sample.With measure the pitting potential of 304 stainless steels in the non-blank-white water sample with quadrat method, measurement result sees Table 1.
4, compare the pitting potential of stainless steel in non-blank-white water sample and blank water sample.As can be seen from Table 1, add anti-incrustation corrosion inhibitor a, b and c in the blank water sample 1 after, the pitting potential of 304 stainless steel electrodes does not all have marked change, but in blank water sample 2, distinguishes apparent in viewly, the resolution of blank water sample 2 is than blank water sample 1 height.Anti-incrustation corrosion inhibitor a makes 304 stainless pitting potential mean values about 150mV that risen, and anti-incrustation corrosion inhibitor b and c are remarkable inadequately to the influence of 304 stainless pitting potentials.Therefore, can judge that anti-incrustation corrosion inhibitor a has tangible corrosion inhibition to 304 stainless steels; Anti-incrustation corrosion inhibitor b and c do not make significant difference to 304 Corrosion Resistance of Stainless Steels.
The pitting potential Eb mV (SCE) of table 1 304 stainless steel electrodes in difference cooling water sample
| Water sample | The cooling water sample | E b1 | E b2 | E b3 | E bMean value | Deviation s |
| 1 | Blank water sample 1 | 100 | 100 | 100 | 1005 | 1.53 |
| 2 | Blank water sample 1 adds anti-incrustation corrosion inhibitor a 35mg/L | 100 | 100 | 101 | 1006 | 3.51 |
| 3 | Blank water sample 1 adds anti-incrustation corrosion inhibitor b 60mg/L | 990 | 101 | 1003 | 17.7 | |
| 4 | Blank water sample 1 adds anti-incrustation corrosion inhibitor c 40mg/L | 101 | 101 | 1014 | 3.54 | |
| 5 | Blank water sample 2 | 617 | 604 | 560 | 594 | 29.9 |
| 6 | Blank water sample 2 adds anti-incrustation corrosion inhibitor a 35mg/L | 700 | 797 | 737 | 745 | 48.9 |
| 7 | Blank water sample 2 adds anti-incrustation corrosion inhibitor b 60mg/L | 630 | 614 | 630 | 625 | 9.24 |
| 8 | Blank water sample 2 adds anti-incrustation corrosion inhibitor c 40mg/L | 645 | 635 | 566 | 615 | 43.0 |
And 304 see Table 2 with the rates of corrosion of 316L stainless-steel tube in different cooling water samples with what weight-loss method recorded.By table 2 as seen, stainless rate of corrosion is extremely low, and is almost nil, and the rate of corrosion error is very big, is difficult to differentiate water treatment agent to stainless corrosion influence degree, also is difficult to differentiate the difference of different stainless-steel tube corrosion resisting properties and different quality erosion performance.
The rate of corrosion of the stainless-steel tube that table 2 weight-loss method records in difference cooling water sample
| The water sample sequence number | Stainless-steel tube | The cooling water sample | 30 days weight loss g | Rate of corrosion mm/a | Deviation s mm/a |
| 1 | 304 | Blank water sample 1 | 0.00020 | 0.00007 | 0 |
| 2 | 304 | Blank water sample 1 adds anti-incrustation corrosion inhibitor a 35mg/L | 0.00020 | 0.00007 | 0.00005 |
| 4 | 304 | Blank water sample 1 adds anti-incrustation corrosion inhibitor c 40mg/L | 0.00010 | 0.00003 | 0.00005 |
| 5 | 304 | Blank water sample 2 | 0.00005 | 0.00002 | 0.00002 |
| 6 | 304 | Blank water sample 2 adds anti-incrustation corrosion inhibitor a 35mg/L | 0.00010 | 0.00003 | 0 |
| 8 | 304 | Blank water sample 2 adds anti-incrustation corrosion inhibitor c 40mg/L | 0.00010 | 0.00003 | 0.00005 |
| 1 | 316L | Blank water sample 1 | 0.00010 | 0.00004 | 0.00005 |
| 5 | 316L | Blank water sample 2 | 0.00010 | 0.00004 | 0 |
[notes]: weight loss and rate of corrosion are the mean value of a plurality of data.
Embodiment 2, evaluate four kinds of water treatment agents are used the stainless-steel tube corrosion resisting property to condenser in the W power plant cooling water influence.
The chilled water of the original unit condenser of W power plant all is a single flow, in short supply day by day along with water resource, and for the using water wisely reasonable use of water, the chilled water of newly-built unit condenser has made into circulating, and the cooling tube of condenser has also made 304 stainless-steel tubes into by copper pipe.This factory and water treatment agent supplier require to evaluate four kinds of water treatment agents are used the stainless-steel tube corrosion resisting property to condenser in this factory's chilled water influence.Estimation steps is as follows:
1, with the chilled water water treatment agent influence of this medicament to the stainless steel corrosion resisting property represented in the influence of pitting resistance of stainless steel.
2, select 1～3 kind of blank water sample, the principal ingredient of blank water sample sees Table 3.Measure the pitting potential of 304 stainless steels in blank water sample, measurement result sees Table 4.
The principal ingredient of the blank water sample of table 3
| pH | Cl - mg/l | SO 4 2- mg/l | Positive phosphorus PO 4 3- mg/l | Total phosphorus PO 4 3- mg/l | Explanation | |
| Blank water sample 3 | 7.53 | 70 | 92 | River, the former water of chilled water | ||
| Blank water sample 4 | 200 | 200 | Recirculated cooling water, no water treatment agent | |||
| Blank water sample 5 | 8.54 | 200 | 213 | 2.7 | 2.9 | Recirculated cooling water has other water treatment agent |
3, in above-mentioned blank water sample, add water treatment agent d, e, f and the g that will evaluate of normal concentration, make the non-blank-white water sample.Water treatment agent d is an organic bromine class Biocidal algae-killing agent, orange liquid, and manufacturer provides; Water treatment agent e is the Biocidal algae-killing agent that organic bromine chlorine mixes, white solid, and active component＞80%, manufacturer provides; Water treatment agent f is the biocide that is formed by acid amides addition product, modified fatty amine and synthetic amine compatibility, yellow liquid, and power plant provides; Water treatment agent g is the anti-incrustation corrosion inhibitor that is formed by monomer composite reagents such as organic phosphine class and polycarboxylic acids, yellow liquid, and power plant provides.With measuring the pitting potential of stainless steel in the non-blank-white water sample that will evaluate with quadrat method, measurement result sees Table 4.
The pitting potential mV (SCE) of table 4 304 stainless steels in difference cooling water sample
| The water sample sequence number | Water quality | E b1 | E b2 | E b3 | Average E b | Deviation s |
| 1 | Blank water sample 3 | 998 | 993 | 996 | 3.54 | |
| 2 | Blank water sample 3 is with water treatment agent d 40mg/L | 992 | 998 | 995 | 4.24 | |
| 3 | Blank water sample 3 is with water treatment agent e 20mg/L | 998 | 996 | 999 | 998 | 1.53 |
| 4 | Blank water sample 3 is with water treatment agent g 30mg/L | 991 | 1005 | 998 | 9.9 | |
| 5 | Blank water sample 4 | 595 | 575 | 647 | 606 | 37.2 |
| 6 | Add water treatment agent d 40mg/L in the blank water sample 4 | 496 | 508 | 513 | 506 | 8.74 |
| 7 | Add water treatment agent e 20mg/ L in the blank water sample 4 | 491 | 456 | 460 | 469 | 19.2 |
| 8 | Add water treatment agent f 20mg/L in the blank water sample 4 | 750 | 752 | 751 | 1.41 | |
| 9 | Blank water sample 3 is with water treatment agent g 30mg/L | 920 | 920 | 996 | 945 | 43.88 |
| 10 | Blank water sample 5 | 910 | 910 | 915 | 912 | 2.89 |
| 11 | Add water treatment agent d 40mg/L in the blank water sample 5 | 912 | 908 | 905 | 908 | 3.51 |
4, compare the pitting potential of stainless steel in non-blank-white water sample and blank water sample.As seen from Table 4, in blank water sample 3 and 5, water treatment agent d is not remarkable to the influence of 304 stainless pitting potentials, and in blank water sample 4, water treatment agent d makes the 304 stainless pitting potentials 100mV that descended; In blank water sample 3, water treatment agent e is not remarkable to the influence of 304 stainless pitting potentials, and in blank water sample 4, water treatment agent e makes 304 stainless pitting potentials about 140mV that descended; In blank water sample 4, water treatment agent f makes the 304 stainless pitting potentials 145mV that risen; In blank water sample 3, water treatment agent g is not remarkable to the influence of 304 stainless pitting potentials, and in blank water sample 4, water treatment agent g makes 304 stainless pitting potentials about 340mV that risen.Therefore can judge: water treatment agent d has the corrosion facilitation to 304 stainless steels in blank water sample 4, in blank water sample 3 and 5 304 Corrosion Resistance of Stainless Steels are not made significant difference; Water treatment agent e has the corrosion facilitation to 304 stainless steels in blank water sample 4, in blank water sample 3 304 Corrosion Resistance of Stainless Steels are not made significant difference; Water treatment agent f has tangible corrosion inhibition to 304 stainless steels; Water treatment agent g has tangible corrosion inhibition to 304 stainless steels, and water treatment agent g to 304 stainless corrosion inhibitions greater than water treatment agent f.
The present invention can comprise that other does not depart from the concrete form of the present invention's spirit or its essential characteristic.Therefore, some embodiments at this only are used for explanation, be not construed as limiting the invention the scope of the invention of determining by the description of claims rather than front and all be included in claims in meaning of claims and all changes in the full scope of equivalents.
Claims (2)
1, a kind of chilled water water treatment agent is to the assessment method of stainless steel corrosion resisting property influence, be characterised in that with the chilled water water treatment agent influence of pitting resistance of stainless steel is characterized the influence of this water treatment agent to the stainless steel corrosion resisting property, its step is to measure earlier pitting potential Ea and the Eb of stainless steel in blank water sample and the non-blank-white water sample in the aqueous treatment agent respectively, compare these two kinds of pitting potentials then, if Eb＞Ea judges that then this water treatment agent has corrosion inhibition to this stainless steel under this concentration; Otherwise then judge the corrosion facilitation is arranged; If these two kinds of pitting potentials do not have significant difference, judge that then this water treatment agent does not make significant difference to this kind Corrosion Resistance of Stainless Steels under this kind concentration; The pitting potential of tested stainless steel in blank water sample is in 300～900mV scope.
2, assessment method according to claim 1 is characterized in that the pitting potential of tested stainless steel in blank water sample is 580 ± 100mv.
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| CN 03115664 CN1189731C (en) | 2003-03-06 | 2003-03-06 | Method for evaluating the affection of water treatment agent to corrosion-resistance of stainless steel |
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| CN1189731C true CN1189731C (en) | 2005-02-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103852415A (en) * | 2014-03-18 | 2014-06-11 | 太原理工大学 | Method for evaluating corrosion resistance of chromized P110 oil sleeve steel by using surface fractal dimensions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374845C (en) * | 2005-09-01 | 2008-03-12 | 复旦大学 | Method for evaluating pitting resistance performance of material |
| CN101439912B (en) * | 2008-12-19 | 2010-10-20 | 上海依科绿色工程有限公司 | Water treatment technology of vehicle body welding process circulating cooling water system |
| JP5830910B2 (en) * | 2011-04-12 | 2015-12-09 | Ｊｆｅスチール株式会社 | Method for evaluating the corrosion resistance of the contents of cans |
| CN103674824B (en) * | 2013-12-04 | 2016-01-20 | 南京钢铁股份有限公司 | Medium simulated solution and select the method for hydraulic support steel based on pitting resistance |
| CN104502262B (en) * | 2014-11-26 | 2017-01-25 | 上海电力学院 | Method for obtaining pitting potential of stainless steel in cooling water and waste-heat water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103852415A (en) * | 2014-03-18 | 2014-06-11 | 太原理工大学 | Method for evaluating corrosion resistance of chromized P110 oil sleeve steel by using surface fractal dimensions |
| CN103852415B (en) * | 2014-03-18 | 2016-04-13 | 太原理工大学 | The corrosion proof method of chromising P110 oil bushing steel is evaluated with Surface Fractal Dimension |
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Assignee: SHENZHEN XIETONG POWER TECHNOLOGY CO., LTD. Assignor: Liang Lei Contract record no.: 2011440020307 Denomination of invention: Method for evaluating the affection of water treatment agent to corrosion-resistance of stainless steel Granted publication date: 20050216 License type: Exclusive License Open date: 20030806 Record date: 20110811 |
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