CN104925992A - Anti-corrosion method for inner cooling water system of engine - Google Patents
Anti-corrosion method for inner cooling water system of engine Download PDFInfo
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- CN104925992A CN104925992A CN201510316089.7A CN201510316089A CN104925992A CN 104925992 A CN104925992 A CN 104925992A CN 201510316089 A CN201510316089 A CN 201510316089A CN 104925992 A CN104925992 A CN 104925992A
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- deoxygenator
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Abstract
The invention provides an anti-corrosion method for an inner cooling water system of an engine. According to the anti-corrosion method, a deoxidation system and a novel mixed-bed treatment system are related, wherein the deoxidation system comprises an H2 rotor flow meter, an intermediate mixing water tank, a water rotor flow meter, a deaerator and a dissolved oxygen analyzer; the novel mixed-bed treatment system comprises Na-type ion exchange resin, H-type ion exchange resin and OH-type ion exchange resin. The anti-corrosion method is characterized in that inner cooling water conveyed by an inner cooling water pump is completely dissolved and mixed with H2 passing through the H2 rotor flow meter in the intermediate mixing water tank; the mixture enters the deaerator through the water rotor flow meter; finally, the deoxidated inner cooling water enters the novel mixed-bed treatment system through a resin trapper. Through the adoption of the anti-corrosion method, the pH value of the inner cooling water in the engine can exceed 7.5 for long, and the conductivity and the dissolved oxygen content are lower than 2.0 [mu]S/cm and 10 [mu]g/L respectively; furthermore, the purpose of protecting the inner cooling water system of the engine from corrosion can be fulfilled. The anti-corrosion method is economical, simple, convenient, safe and reliable.
Description
Technical field
The present invention relates to a kind of anti-corrosion method of electric generator inner cooling water system, particularly a kind of anti-corrosion method of electric generator inner cooling water system tubular copper conductor.
Background technology
At present, domestic super-critical and ultra super-critical power unit generator all adopts Water hydrogen formula cooling system, and stator adopts water-cooled, and rotor and iron core adopt hydrogen_cooling.Cause tubular copper conductor corrosion and scaling because inner cold water water quality is defective in recent years, blockage problem happens occasionally.Tubular copper conductor is corroded and will produces extremely serious consequence, the lighter makes the rising of water coolant specific conductivity, leakage current increases, electrical insulation properties reduces, thermal conduction is obstructed, generator coil temperature rise is caused to increase, corrosion product even can block tubular copper conductor and cause coil overheated, increase falls in hydraulic pressure, affects generator output; Severe one will cause generator to be forced to shutdown inspection, burn generator.Therefore, slowing down and prevent electric generator inner cooling water copper conductor from corroding is the important means ensureing that engine health runs.
The domestic and international anti-corrosion measure taked tubular copper conductor is at present roughly divided into four classes: 1. prevent oxygen and carbon dioxide from entering water-cooling generator; 2. adopt and openly change water running or bypass ion-exchange (little mixed bed) method; 3. basifier process is added; 4. inhibiter process is added.Although these four kinds for the treatment of processs once obtained some effects, also exposed many problems.As the airtight isolated water cooling system of generator generally adopted, in order to alleviate the corrosion of copper conductor, the dissolved oxygen in water coolant is reduced to below 100ug/L abroad, this method can increase the burden of system assembling and running maintenance; More domestic power plant adopts continuous blow-down, adjusts the method for pH by changing water ammonification simultaneously in a large number, although copper content can be made to decrease, effect is also not bery desirable, and continuous blow-down significantly increases supplementary feed; Inhibiter MBT is added in water coolant, although preservative effect is better, but because MBT itself is water insoluble, need alkali dissolution be added, but easily increase water coolant specific conductivity after adding alkali, when pH value is slightly low, MBT can separate out and be attached on copper conductor inwall, become a kind of yellow fluffy settling, run in this case for a long time, also can block copper conductor.
Therefore seek the etching problem that a kind of more economic, easy, safe and reliable method solves water-cooling generator and be still a problem demanding prompt solution.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, a kind of anti-corrosion method of electric generator inner cooling water system is provided, the method can not only remove the dissolving oxygen and carbon dioxide in electric generator inner cooling water, and pH value and the specific conductivity of inner cold water can be regulated, make it to reach acceptability limit, reach the object preventing electric generator inner cooling water system corrosion.The method also has that equipment is simple, expense maintenance is little, empty calory consumption, residual oxygen are low, can not increase salt grades advantage.
For realizing above object, this invention takes following technical scheme.
The present invention mainly comprises deaerating type of cycles and novel mixed bed treatment system.Wherein, deaerating type of cycles comprises H
2spinner-type flowmeter, middle mixing tank, water spinner-type flowmeter, deoxygenator and dissolved oxygen analyser; Na type ion exchange resin, H type Zeo-karb and OH type ion exchange resin is had in novel mixed bed treatment system.
According to deoxidation method used in the present invention, its deoxygenation principle passes into hydrogen in inner cold water, makes inner cold water contain certain dissolved hydrogen.In deoxygenator, make contact medium with heterogeneous solid catalyst, make oxygen in water be reduced to H
2o, in the inner cold water of deoxygenator, the mass concentration of dissolved oxygen can be controlled in 10 below μ g/L, effectively can control the corrosion of copper conductor.Heterogeneous solid catalyst in deoxygenator, using gac as carrier, while energy absorbed portion impurity, also can make heterogeneous solid catalyst be evenly distributed in deoxygenator.Its principle is: pass into hydrogen to containing in the inner cold water of dissolved oxygen, because heterogeneous solid catalyst is to the high adsorption capacity of hydrogen, adsorbable a large amount of hydrogen, simultaneously also can adsorb oxygen, under its katalysis, the hydrogen that is adsorbed on surface and oxygen can be impelled to react generation water.
Heterogeneous solid catalyst of the present invention is a kind of elemental metals, the operating parameter of deoxygenator is as follows: optimum operation filtering velocity is 20 ~ 60m/h, optimum operation temperature is 15 ~ 50 DEG C, the water conservancy residence time should not be less than 1min, deoxygenation post height should be not less than 600mm, pH is 3 ~ 9, and absorption pressure is 0.1 ~ 0.12MPa.
According to novel mixed bed treatment system process inner cold water used in the present invention, following ionic reaction can be there is:
nRNa+M
n+→RnM+nNa
+
nRH+M
n+→RnM+nH
+
HCO
3-+ROH→RHO
3+OH
-
The product of above-mentioned ionic reaction can continue to react, final generation water and sodium hydroxide.Be V by controlling the volume ratio of three kinds of resins
rNa: V
rH: V
rOH=1:0. 2 ~ 0.8:2.5 ~ 3.5, can discharge the NaOH of trace, make water-cooling generator be slight alkalinity, suppress the corrosion of inner cold water tubular copper conductor, can remove again the foreign ion in water.
Adopt water-cooling generator anti-corrosion method provided by the invention, dissolved oxygen in electric generator inner cooling water can be down to below 10ug/L on the one hand, pH value and specific conductivity remain on more than 7.5 and 2.0 below μ S/cm respectively for a long time, inner cold water water quality can also be made simultaneously to keep qualified stable, prevent the corrosion that water-cooling generator causes because water quality is defective.
Compared with prior art, the present invention is adopted to have following unique advantage.
1. can realize deoxygenation (≤15 DEG C) at normal temperatures, and deoxygenation speed of response fast (1min can react completely), oxygen removal efficiency high (≤10 μ g/L), reduces the possibility of tubular copper conductor and oxygen generation corrosion reaction.
2. not needing to add any medicament can make inner cold water be in slight alkalinity (>=7.5) for a long time, makes the copper part of water-cooling generator be in self-passivation state for a long time, reduces the corrosion of water-cooling generator.
3., while the oxygen removed in inner cold water and carbonic acid gas, other foreign ions can also be removed (as Cu
2+), make the dissolved oxygen of inner cold water, pH value, specific conductivity (≤1.0 μ S/cm), Cu
2+deng simultaneously up to standard, reduce the risk that water-cooling generator stands to corrode.
4. the present invention is simple to operate, can realize operate continuously, and can not produce by product, does not also need the equipment increasing electric generator inner cooling water system simultaneously, makes system more economical, stable, simple, reliable.
Accompanying drawing explanation
Accompanying drawing 1 is a kind of anti-corrosion method system schematic of electric generator inner cooling water system.
Embodiment
The invention provides a kind of anti-corrosion method of electric generator inner cooling water system, the method comprises deaerating type of cycles and novel mixed bed treatment system, and concrete device comprises H
2spinner-type flowmeter, middle mixing tank, water spinner-type flowmeter, deoxygenator and dissolved oxygen analyser, resin catcher, novel mixed bed treatment system and conductivitimeter, pH meter.
Continuous process of the present invention is: the inner cold water of coming through inner cold water pump delivery with through H
2the H of spinner-type flowmeter
2fully dissolve mixing at middle mixing tank, then enter deoxygenator by middle water pump through inner cold water spinner-type flowmeter, the inner cold water after last deoxygenation enters novel mixed bed treatment system after resin catcher.Wherein, be equipped with conductivitimeter and pH meter in novel mixed bed treatment system outlet, deoxygenator outlet is provided with dissolved oxygen analyser.
Preparation example below and embodiment contribute to those of ordinary skill in the art and more fully understand the present invention, but do not limit to its scope.
Preparation example 1
The invention provides the preparation method of fill in deoxygenator.
By the solution containing heterogeneous solid catalyst by activated carbon column, carry out filtering, wash and obtain heterogeneous solid catalyst/activated-carbon catalyst.The wherein H of heterogeneous solid catalyst acidic solution
+concentration is 0.5 ~ 1.2mol/L, and filtration time is generally 50 ~ 100min.
Preparation example 2
This patent provides the treatment process of hybrid resin in novel mixed bed treatment system.
New resin, before with medicament process, first must make resin fully expand with water, with water rinse resin, removes broken resin wherein and mechanical impurity.If resin has taken off water in transport or storage process, then directly can not put into water, the NaCl first applying 10% soaks, then rinses with water, prevents resin swelling from breaking.Carry out pre-treatment with acid, alkaline solution before the use, the soluble impurity in removing resin, can improve resin stability after pre-treatment, and all right activated resin, improves resin operating capacity.
The process of Na type ion exchange resin: adopt the NaCl solution of 1mol/L to carry out immersion 24 hours, then wash with pure water, until instill AgNO in the washings taken out
3till there is not muddiness in solution.
H type ion exchange resin treatment: adopt the HCl solution of 1mol/L to carry out immersion 24 hours, then wash with pure water, till instilling the not aobvious redness of tropeolin-D instruction solution in the washings taken out.
The process of OH type ion exchange resin: the HCl solution soaking 24h first using 1mol/L, washs with pure water, instill the not aobvious redness of tropeolin-D instruction solution in the washings taken out till.Then 24 hours are soaked by the NaOH solution of 1mol/L, till instilling phenolphthalein instruction in the washings taken out solution being colourless.
Below in conjunction with embodiment, the present invention is made a more detailed description.
Embodiment 1
The present embodiment is used for illustrating the anti-corrosion method of electric generator inner cooling water of the present invention.
Make deoxygenation post in heterogeneous solid catalyst preparation example 1 prepared/gac filler sleeve, be then arranged in exchange column and become deoxygenator, the height of deoxygenator is 0.8m, and flow velocity is 2.5m
3/ h, hydrogen dosage throws hydrogen amount slightly larger than theory, and hydrogen pressure is suitable with inner cold water pressure.
Na type ion exchange resin preparation example 2 obtained, H type ion exchange resin, OH type ion exchange resin are by V
rNa: V
rH: V
rOHthe ratio of=1:0.4:3.1 mixes, and obtains hybrid resin.Be filled in ion exchange column by the hybrid resin obtained, and pad one deck filter screen on OH type ion exchange resin, separate at positive resin layer polyethylene board, the amount of fill of hybrid resin is 0.1m
3, then make de-mineralized water with 2.5 m
3the flow velocity of/h is by novel mixed bed treatment system of the present invention, until specific conductivity is less than 0.3 μ S/cm ability commencement of commercial operation.
By accompanying drawing 1, pump, under meter, valve, deoxygenator, novel mixed bed treatment system and various chemical instruments are connected, and be incorporated in electric generator inner cooling water circulation system.
PH=5 ~ 7 of the inner cold water that generator is discharged, specific conductivity=1 ~ 5 μ S/cm, dissolved oxygen=30 ~ 100 μ g/L, flow velocity=2.5m
3/ h.The duration of contact of inner cold water and deoxygenator is 3min, and Contact Temperature is 45 DEG C, and after entering novel combination treatment, duration of contact is 20min with it, and Contact Temperature is 40 DEG C.Electric generator inner cooling water cycle after process enters generator unit stator and cools, continuous circulation like this uses inner cold water, every 1 day, with the dissolved oxygen of dissolved oxygen analysis-e/or determining deoxygenator outlet, measure specific conductivity and the pH value of novel mixed bed treatment system outlet inner cold water with conductivitimeter and pH meter.After 300 days, the dissolved oxygen of deoxygenator outlet is 8.15 μ g/L, and the pH of novel hybrid processor water outlet is 8.31, and specific conductivity is 0.88 μ S/cm.
Embodiment 2
The present embodiment is used for illustrating the anti-corrosion method of electric generator inner cooling water of the present invention.
Make deoxygenation post in heterogeneous solid catalyst preparation example 1 prepared/gac filler sleeve, be then arranged in exchange column and become deoxygenator, the height of deoxygenator is 1.0m, and flow velocity is 2.5m
3/ h, hydrogen dosage throws hydrogen amount slightly larger than theory, and hydrogen pressure is suitable with inner cold water pressure.
Na type ion exchange resin preparation example 2 obtained, H type ion exchange resin, OH type ion exchange resin are by V
rNa: V
rH: V
rOHthe ratio of=1:0.6:3.0 mixes, and obtains hybrid resin.Be filled in ion exchange column by the hybrid resin obtained, and pad one deck filter screen on OH type ion exchange resin, separate at positive resin layer polyethylene board, the amount of fill of hybrid resin is 0.1m
3, then make de-mineralized water with 2.5 m
3the flow velocity of/h is by novel mixed bed treatment system of the present invention, until specific conductivity is less than 0.3 μ S/cm ability commencement of commercial operation.
By accompanying drawing 1, pump, under meter, valve, deoxygenator, novel mixed bed treatment system device and various chemical instruments are connected, and be incorporated in electric generator inner cooling water circulation system.
PH=5 ~ 7 of the inner cold water that generator is discharged, specific conductivity=1 ~ 5 μ S/cm, dissolved oxygen=30 ~ 100 μ g/L, flow velocity=2.5m
3/ h.The duration of contact of inner cold water and deoxygenator is 3min, and Contact Temperature is 45 DEG C, and after entering novel mixed bed treatment system, duration of contact is 20min with it, and Contact Temperature is 40 DEG C.Electric generator inner cooling water cycle after process enters generator unit stator and cools, continuous circulation like this uses inner cold water, every 1 day, with the dissolved oxygen of dissolved oxygen analysis-e/or determining deoxygenator outlet, measure specific conductivity and the pH value of novel mixed bed treatment system outlet inner cold water with conductivitimeter and pH meter.After 180 days, the dissolved oxygen of deoxygenator outlet is 0.63 μ g/L, and the pH of novel mixed bed treatment system water outlet is 8.52, and specific conductivity is 0.56uS/cm.
Embodiment 3
The present embodiment is used for illustrating the anti-corrosion method of electric generator inner cooling water of the present invention.
Make deoxygenation post in heterogeneous solid catalyst preparation example 1 prepared/gac filler sleeve, be then arranged in exchange column and become deoxygenator, the height of deoxygenator is 1.0m, and flow velocity is 2.5m
3/ h, hydrogen dosage throws hydrogen amount slightly larger than theory, and hydrogen pressure is suitable with inner cold water pressure.
The Na type ion exchange resin that preparation example 2 is obtained, H type ion exchange resin, OH type ion exchange resin V
rNa: V
rH: V
rOHthe ratio of=1:0.5:3.0 mixes, and obtains hybrid resin.Be filled in ion exchange column by the hybrid resin obtained, and pad one deck filter screen on OH type ion exchange resin, separate at positive resin layer polyethylene board, the amount of fill of hybrid resin is 0.1m
3, then make de-mineralized water with 2.5 m
3the flow velocity of/h is by novel mixed bed treatment system of the present invention, until specific conductivity is less than the commencement of commercial operation of 0.3uS/cm ability.
By accompanying drawing 1, pump, under meter, valve, deoxygenator, novel mixed bed treatment system and various chemical instruments are connected, and be incorporated in electric generator inner cooling water circulation system.
PH=5 ~ 7 of the inner cold water that generator is discharged, specific conductivity=1 ~ 5 μ S/cm, dissolved oxygen=30 ~ 100 μ g/L, flow velocity=2.5m
3/ h.The duration of contact of inner cold water and deoxygenator is 3min, and Contact Temperature is 45 DEG C, and after entering novel mixed bed treatment system, duration of contact is 20min with it, and Contact Temperature is 40 DEG C.Electric generator inner cooling water cycle after process enters generator unit stator and cools, continuous circulation like this uses inner cold water, every 1 day, with the dissolved oxygen of dissolved oxygen analysis-e/or determining deoxygenator outlet, measure specific conductivity and the pH value of novel mixed bed treatment system outlet inner cold water with conductivitimeter and pH meter.After 180 days, the dissolved oxygen of deoxygenator outlet is 0.30 μ g/L, and the pH of novel mixed bed treatment system water outlet is 8.60, and specific conductivity is 0.30 μ S/cm.
Claims (3)
1. an anti-corrosion method for electric generator inner cooling water system, comprises deaerating type of cycles and novel mixed bed treatment system, and deaerating type of cycles and novel mixed bed treatment system are combined into a kind of protective system of electric generator inner cooling water system, it is characterized in that, deaerating type of cycles comprises H
2spinner-type flowmeter, middle mixing tank, water spinner-type flowmeter, deoxygenator and dissolved oxygen analyser, the inner cold water of coming through inner cold water pump delivery with through H
2the H of spinner-type flowmeter
2fully dissolve mixing at middle mixing tank, then enter deoxygenator by middle water pump through inner cold water spinner-type flowmeter, the inner cold water after last deoxygenation enters novel mixed bed treatment system after resin catcher.
2. method according to claim 1, in deoxygenator, heterogeneous solid catalyst is elemental metals, carrier is gac, in novel mixed bed treatment system, Na type ion exchange resin, H type Zeo-karb and OH type ion exchange resin are gel-type ion-exchange resin, and the volume ratio of three kinds of resins is V
rNa: V
rH: V
rOH=1:0. 2 ~ 0.8:2.5 ~ 3.5.
3. method according to claim 1, the optimum operation filtering velocity of deoxygenator is 20 ~ 60m/h, and optimum operation temperature is 15 ~ 50 DEG C, and hydraulic detention time should be greater than 1min, and deoxygenation post height should be greater than 600mm, and pH is 3 ~ 9, and absorption pressure is 0.1 ~ 0.12MPa.
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|---|---|---|---|
| CN201510316089.7A CN104925992A (en) | 2015-06-11 | 2015-06-11 | Anti-corrosion method for inner cooling water system of engine |
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|---|---|---|---|
| CN201510316089.7A CN104925992A (en) | 2015-06-11 | 2015-06-11 | Anti-corrosion method for inner cooling water system of engine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112921333A (en) * | 2021-01-21 | 2021-06-08 | 武汉大学 | Internal-cooling water ion exchange slow-release micro-acidification flexible online cleaning system and method for failure passivation film of hollow copper conductor of generator |
| CN114959676A (en) * | 2022-03-29 | 2022-08-30 | 武汉大学 | System and method for in-service self-passivation of cold water and oxygen enhanced hollow copper conductor in generator |
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| CN112921333A (en) * | 2021-01-21 | 2021-06-08 | 武汉大学 | Internal-cooling water ion exchange slow-release micro-acidification flexible online cleaning system and method for failure passivation film of hollow copper conductor of generator |
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Application publication date: 20150923 |