CN114807953B - Pulse-flexible pickling system and method for corrosion products of hollow copper wires of generator - Google Patents
Pulse-flexible pickling system and method for corrosion products of hollow copper wires of generator Download PDFInfo
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- CN114807953B CN114807953B CN202210418754.3A CN202210418754A CN114807953B CN 114807953 B CN114807953 B CN 114807953B CN 202210418754 A CN202210418754 A CN 202210418754A CN 114807953 B CN114807953 B CN 114807953B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/025—Details of the apparatus, e.g. linings or sealing means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/027—Associated apparatus, e.g. for pretreating or after-treating
- C23G3/029—Associated apparatus, e.g. for pretreating or after-treating for removing the pickling fluid from the objects
Abstract
The invention discloses a pulse-flexible pickling system and method for corrosion products of hollow copper wires of a generator. Under the condition of not adding a copper substrate corrosion inhibitor, the corrosion product of the hollow copper conductor of the generator is flexibly pickled by using a low-acidity pickling solution, meanwhile, the mass transfer effect of the pickling solution on the corrosion product is enhanced by using gas-water pulse, and the waste liquid formed by pulse-flexible pickling is directly discharged into a living waste water biochemical treatment system of a power plant after the pH value is regulated. The invention can remove corrosion products on the inner surface of the hollow copper wire by using the pickling solution with low concentration under the condition of not adding the copper corrosion inhibitor by coupling gas-water pulse and flexible chemical pickling. The waste liquid generated by pulse-flexible pickling has low content of waste acid and organic matters and low treatment difficulty, and the problems of complex treatment procedures and high cost of the conventional chemical pickling waste liquid are avoided.
Description
Technical Field
The invention relates to a pulse-flexible pickling system and a method for a generator hollow copper wire corrosion product, belonging to the technical field of chemical cleaning engineering of power generation equipment.
Background
The generator is one of main mechanical equipment for producing electric power such as thermal power, nuclear power, hydropower and the like. During operation of the generator, the stator copper wire generates a large amount of heat due to the action of the strong electromagnetic field. In order to ensure the normal operation of the generator, cooling water is generally used for cooling the heating stator through the hollow copper wire. Since the inner surface of the hollow copper wire is in direct contact with the inner cold water, corrosion of the copper wire occurs in the inner cold water. The localized deposition of corrosion products can clog hollow copper wire waterways, thereby causing a drop in cooling water flow, localized overheating, and even unplanned shutdown of the generator (She Chunsong. Micro copper corrosion control principles in pure water and applied technical research [ D ]. Shanghai: university, 2002;M.SVOBODA,T.BAUER,Corrosion and deposits in water-cooled generator stator windings: part 4:operating experience with flow restrictions in stator cooling water systems[J ]. Powerplant Chemistry,2019,21:62-72; at Hua Jiang, meng Xinjing, ge Gonghua. Corrosion and control in inner cold water [ J ]. Corrosion and protection of stator copper coils, 2021,42 (10): 61-67).
In order to avoid abnormal system and even production safety accidents caused by corrosion product accumulation, when the running state of the system reaches the cleaning criterion condition, the hollow copper conductor of the generator needs to be cleaned to remove corrosion products (BAUER T, SVOBODA M, SVOBODAR.Corrosion and deposits in water-cooled generator stator windings: part 3:removal of flow restrictions[J ]. PowerPlant Chemistry,2019,21 (1): 10-22; wang Chong, liu, he Rong, etc.. A method for treating blockage of a stator bar of an internal water cooled generator [ J ]. Electric safety technique, 2009,11 (03): 65-67). In order to solve the abnormal states of running flow reduction, inlet pressure increase and the like of a cold water system in a certain power plant, wang Kun and the like wash and acid wash the corrosion coil by adopting a water hammer flushing-acid washing process. In the water hammer flushing process, the pressure is increased to 0.5-0.6 MPa by inflating the loop, then the pressure is suddenly released, the copper wire is forcefully flushed by utilizing the 'water hammer' effect generated by the pressure release, and the flow path is dredged and blocked. After the water hammer flushing is finished, 2% -4% of high-concentration compound acid is adopted to carry out chemical acid washing on the copper wire. In order to avoid corrosion of the high-concentration composite acid to the copper substrate, 200mg/L to 600mg/L of high-concentration copper corrosion inhibitor is added into the pickling solution. After the cleaning is completed, the running state of the system is recovered to be normal. Song Xiaoning and the like, and a compound pickling formula taking sulfamic acid as main functional organic acid and benzotriazole as a copper corrosion inhibitor is obtained by adopting small test screening. They then washed the corrosion blocked internal cooling water system according to the "water rinse-acid wash-water rinse" process. In situ cleaning results indicate that this process effectively removes copper corrosion products within the system. After the cleaning is completed, the cold water flow in the system is recovered to be normal, and the over-temperature phenomenon of the stator copper wire rod is eliminated (Song Xiaoning, feng Likui, yan Min, and the like; chemical cleaning of the cold water system in the generator [ J ]. Cleaning the world, 2012,28 (10): 12-15).
The main problem of the current chemical pickling method is that the concentration of acid in pickling solution is high, and the treatment difficulty of waste liquid generated after pickling is extremely high. Relevant standards prescribe that the corrosion rate of the hollow copper wire in the chemical acid washing process should be lower than 1g/m 2 H (DL/T957-2017 condenser chemical cleaning and film formation guide of thermal power plant [ S ]]Beijing, china electric Press, 2017; HG/T2387-2007 Industrial Equipment chemical cleaning quality Standard [ S]Beijing, chemical industryVersion society, 2007). To meet this requirement, high concentrations of organic corrosion inhibitors must be added simultaneously to the chemical pickling solutions currently in use to inhibit the corrosive effects of high concentrations of acid on bare copper substrates. This results in a waste pickle liquor containing a high concentration of spent acid and organics. With the increasingly strict requirements of external drainage and environmental protection of the power plant at present, the pickling waste liquid can be discharged after being treated to be qualified (Zhong Qunlian, yang Yang, zhou Zhen, etc.. The research of the chemical cleaning waste water treatment technology is advanced [ J)]Instructions on Shanghai electric power university, 2019,35 (03): 261-266). The waste acid and organic corrosion inhibitor in the chemical acid washing waste liquid of the hollow copper wire copper oxide have high concentration and complex components, and part of substances have stable chemical properties and certain biotoxicity. This makes the treatment of copper wire chemical pickling waste liquid very difficult, with high costs.
The gas-water pulse cleaning is a physical cleaning technology capable of effectively flushing and stripping sediment in pipelines, and is applied to pipeline cleaning in various fields (Wang Yang, zhu Qiongyu. Domestic drinking water secondary water supply facility cleaning technology and development [ J ]. Water purifying technology, 2020,39 (S1): 88-91; jiang Yajun, du Kun, wei Chenqian, etc.. Railway tunnel drainage blind pipe crystallization deposition dredging cleaning technology [ J ]. Tunnel and rail traffic, 2020 (4): 9-13; ruin. Oil and gas pipeline pulse resonance cleaning technology feasibility experiment research [ J ]. Cleaning world, 2018,34 (12): 7-9). However, the generator hollow copper conductor water flow channel is narrow and the flow direction is complex. The physical cleaning by gas-water pulse alone does not completely remove copper corrosion products (Song Lei.1 000MW generator stator bars chemical cleaning [ J ]. Cleaning world, 2009,25 (9): 9-12). The unremoved corrosion products may redissolve, deposit after the cold water system is put back into operation and are detrimental to the formation of new passivation films.
Disclosure of Invention
The invention aims to solve the problems of the existing chemical cleaning technology for corroding hollow copper wires, and provides a pulse-flexible pickling method for corroding the product of the hollow copper wires of a generator, wherein under the conditions of reducing the acid consumption and not adding a copper corrosion inhibitor, the dissolution of pickling solution to the corrosion product is promoted through the mass transfer synergy of gas-water pulse, and the treatment difficulty of pickling waste liquid is reduced from the source of the pickling method design.
According to the invention, the low-concentration acid solution is used as the pickling agent, the copper substrate corrosion inhibitor is not added, the corrosion product of the hollow copper conductor of the generator is flexibly pickled, meanwhile, the dissolution of the corrosion product by the low-concentration pickling agent is enhanced by coupling gas-water pulse, and the waste liquid generated by pickling is low in concentration of waste acid and organic matters, so that the treatment difficulty of the pickling waste liquid is greatly reduced.
The cross section of the hollow copper wire is narrower, and the water flow cross section is only tens or tens of square millimeters. The corrosion products of the hollow copper wire mainly comprise CuO and Cu 2 The chemical reaction formula of O, in which O and O are dissolved in an acidic solution is as follows:
CuO+2H + →Cu 2+ +H 2 O (1)
Cu 2 O+2H + →2Cu + +H 2 O (2)
the equilibrium relationship of the two chemical reactions at 25 ℃ is as follows:
log[Cu 2+ ]＝7.00-2pH (3)
log[Cu + ]＝-0.65-pH (4)
in Cu form + Or Cu 2+ Is 10 -6 mol/L is the limit of corrosion occurrence, cu at 50 DEG C 2 The pH at which the O film started to dissolve was 5.35, while the pH at which the CuO film started to dissolve was 6.50. The pH value of the pickling solution is lower than 5.35, so that the pickling solution can play a role in dissolving the two copper oxides.
In a first aspect, the invention provides a pulse-flexible pickling system for a generator hollow copper wire corrosion product, which comprises a pickling stock solution water tank, a constant-temperature stirring pickling water tank, a water circulating pump, a pulse device, a generator hollow copper wire, a pure water tank and a waste liquid water tank;
the pickling stock solution water tank is communicated to a first inlet of the constant-temperature stirring pickling water tank; the outlet of the constant-temperature stirring pickling water tank is sequentially connected with a water circulation pump and a generator hollow copper wire, and then is communicated to the second inlet of the constant-temperature stirring pickling water tank through a pipeline to form circulation; a pulse device and a vacuum dryer are sequentially connected to a pipeline between the water circulating pump and the generator hollow copper wire; the pulse device comprises an air compressor and a pulse frequency regulator;
the water circulation pump is also connected to the pure water tank;
and the hollow copper wire outlet pipeline of the generator is communicated to the waste liquid water tank through a branch.
Further, flexible acid liquor is filled in the acid washing stock solution water tank.
Furthermore, the effective components of the flexible acid liquor are mixed organic acid composed of ethylenediamine tetraacetic acid, citric acid and sulfamic acid.
Further, the air compressor is connected with the pulse frequency regulator and then connected to the pipeline.
Further, valves are arranged between the water circulation pump and the outlet of the constant-temperature stirring pickling water tank and between the water circulation pump and the pure water tank; a valve is arranged between the pulse device and the vacuum dryer.
Further, a valve and a pickling liquid sampling valve are arranged on a pipeline between the generator hollow copper wire and the constant-temperature stirring pickling water tank; and a valve is arranged on a pipeline between the generator hollow copper wire and the waste liquid water tank.
In a second aspect, the invention provides a pulse-flexible pickling method by using the system of the first aspect, which is characterized in that under the condition of not adding a copper substrate corrosion inhibitor, a low-acidity pickling solution is used for coupling gas-water pulse enhanced pickling solution to carry out flexible pickling on a generator hollow copper conductor corrosion product;
the method comprises the following steps:
s1, pre-flushing with pure water;
s2, pulse-flexible pickling: the pickling stock solution tank, the constant-temperature stirring pickling tank, the water circulating pump, the pre-rinsed generator hollow copper wire and the waste liquid tank are communicated through a valve; the pH value of the solution in the constant-temperature stirring pickling water tank is about 3.5 by adding flexible acid liquor, and the temperature is kept; starting a water circulation pump to enable the pickling solution to be filled in the whole hollow copper wire; setting a gas-water pulse period according to the corrosion and blockage condition of a copper wire, starting an air compressor and a pulse device, carrying out pulse-flexible circulation pickling, intermittently collecting a pickling liquid sample to determine the copper ion content in the pickling liquid sample, taking the stability of the pickling liquid sample as an index of ending the pulse-flexible circulation pickling, and collecting pickling waste liquid from a waste liquid tank after the pickling is ended;
s3, washing with pure water: the pure water tank, the water circulating pump, the generator hollow copper wire after pickling and the waste liquid tank are communicated through valves; starting a water circulation pump, starting pure water flushing, taking the water outlet of the pure water circulation pump as a pure water flushing ending index, and collecting flushing wastewater by a waste liquid tank;
s4, pulse air sweeping-vacuumizing drying: the pulse device, the vacuum dryer and the generator hollow copper wire after water flushing are communicated through a valve; setting a gas-water pulse period of a pulse frequency regulator, starting pulse gas sweep, taking no obvious accumulated water at an outlet of a copper wire as an ending index of the pulse gas sweep, starting a vacuum dryer, and vacuumizing and drying an empty copper wire;
s5, disposing acid washing waste liquid: and regulating the pH value of the pickling waste liquid in the waste liquid water tank to be neutral by using NaOH solution, and directly discharging the supernatant of the waste liquid into a domestic waste water biochemical treatment system of the power plant.
In step S1, the corrosive hollow copper wire of the generator is washed by pure water in a variable flow manner until the effluent is clear.
Further, in the steps S1 and S4, the pressure of the air compressor is 0.8MPa.
Further, in the step S4, the air-water pulse period of the pulse frequency regulator is 2S.
Further, the flexible pickling means that the acidity of the pickling solution is low, the pH value of the pickling solution is regulated to be about 3.5, and under the condition of the pH value, the pickling solution has slight corrosion effect on the exposed copper substrate because of pickling, so that a copper corrosion inhibitor is not required to be added in the pickling process. Therefore, the waste liquid generated by acid washing has low content of waste acid and organic matters.
Further, the pulse enhanced pickling dissolution refers to the formation of periodic pulse water flow in the corroded hollow copper wire by using high-pressure compressed air, and the pulse water flow aggravates water flow turbulence and increases shearing force, so that the permeation and mass transfer effect of pickling solution on a corrosion product layer is forcefully promoted, and the flexible pickling rate is accelerated.
Further, the treatment of the pickling waste liquid means that the pH value of the pickling waste liquid is regulated to be neutral by adopting a NaOH solution, copper ions in the pickling waste liquid can be completely precipitated under the condition of the pH value, and waste liquid supernatant after the pH value regulation pretreatment can be directly discharged into a domestic wastewater biochemical treatment system of a power plant.
The beneficial effects of the invention are as follows: by adopting the technical scheme, through coupling gas-water pulse and flexible chemical acid cleaning, the corrosion products on the inner surface of the narrow-inner-diameter hollow copper wire can be removed by acid cleaning with low-concentration acid cleaning liquid under the condition of not adding a copper corrosion inhibitor, and the cleaning effect of the narrow-inner-diameter hollow copper wire is greatly improved by the synergistic effect of chemical corrosion and pulse of the acid liquid; the pickling waste liquid can be directly discharged into a domestic wastewater treatment system of a power plant after being subjected to simple pH value adjustment pretreatment, so that the treatment of the pickling waste liquid is simplified from the source.
Drawings
FIG. 1 is a schematic diagram of a pulse-flexible pickling method for corrosion products of hollow copper conductors of a generator according to the present invention.
The method comprises the following steps of 1, pickling a stock solution water tank; 2. stirring and pickling water tank at constant temperature; 3. a water circulation pump; 4. an air compressor; 5. a pulse frequency adjuster; 6. a vacuum dryer; 7. hollow copper wires of the generator; 8. a pure water tank; 9. a waste liquid tank; 10. a bottom discharge valve of the pickling stock solution tank; 11. constant temperature stirring pickling water tank bottom discharge valve; 12. constant temperature stirring pickling water tank water outlet valve; 13. a hollow copper wire inlet valve; 14. constant temperature stirring pickling water tank inlet valve; 15. a pickling solution sampling valve; 16. a pure water tank bottom discharge valve; 17. water outlet valve of pure water tank; 18. waste water tank inlet valve; 19. a waste water tank water outlet valve.
Detailed Description
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1
As shown in fig. 1, the pulse-flexible pickling system for the corrosion products of the hollow copper conductor of the generator comprises a pickling stock solution water tank 1, a constant-temperature stirring pickling water tank 2, a water circulating pump 3, a pulse device, the hollow copper conductor 7 of the generator, a pure water tank 8 and a waste liquid water tank 9.
The pickling stock solution water tank 1 is communicated with a first inlet of the constant-temperature stirring pickling water tank and is provided with a bottom discharge valve 10 of the pickling stock solution water tank. The outlet of the constant temperature stirring and pickling water tank 2 is sequentially connected with a water circulation pump 3 and a generator hollow copper wire 7, and then is communicated to the second inlet of the constant temperature stirring and pickling water tank 2 by a pipeline to form circulation. The pulse device and the vacuum dryer 6 are sequentially connected to a pipeline between the water circulation pump 3 and the generator hollow copper wire 7. The pulse device comprises an air compressor 4 and a pulse frequency regulator 5, wherein the air compressor 4 is connected with the pulse frequency regulator 5 and then connected to a pipeline.
The water circulation pump 3 is also connected to a pure water tank 8.
The outlet pipeline of the generator hollow copper wire 7 is communicated to a waste liquid water tank 9 through a branch.
The pickling stock solution tank is filled with flexible acid liquor. Preferably, the active ingredients of the flexible acid liquor are mixed organic acids consisting of ethylenediamine tetraacetic acid, citric acid and sulfamic acid.
The outlet of the water circulation pump and the outlet of the constant-temperature stirring and pickling water tank are provided with a constant-temperature stirring and pickling water tank water outlet valve 12. And a pure water tank water outlet valve 17 is arranged between the water circulation pump 3 and the pure water tank 8. A hollow copper wire inlet valve 13 is arranged between the pulse device and the vacuum dryer 6.
And a pipeline between the generator hollow copper wire 7 and the constant-temperature stirring pickling water tank 2 is provided with a constant-temperature stirring pickling water tank water inlet valve 14 and a pickling liquid sampling valve 15. A waste water tank water inlet valve 18 is arranged on a pipeline between the generator hollow copper wire 7 and the waste water tank 9.
The constant temperature stirring pickling water tank 2 is also provided with a constant temperature stirring pickling water tank bottom discharge valve 11. The pure water tank 8 is also provided with a pure water tank bottom discharge valve 16. The waste water tank 9 is also provided with a waste water tank outlet valve.
Example 2
If the running state of the internal cooling water system of the generator shows that serious corrosion and blockage of the system occur, the hollow copper conductor corrosion product is subjected to pulse-flexible acid washing by adopting high-frequency pulses, and the method comprises the following steps of:
s1, pre-flushing with pure water: and (3) carrying out variable flow flushing on the corroded hollow copper wire of the generator by using pure water until the effluent is clear.
S2, pulse-flexible pickling: the method comprises the steps of communicating a pickling stock solution water tank 1, a constant-temperature stirring pickling water tank 2, a water circulation pump 3, a pre-rinsed generator hollow copper wire 7 and a waste liquid water tank 9 through pipelines and related valves, adding flexible chemical pickling liquid into the pickling stock solution water tank 1, adding a proper amount of desalted water into the constant-temperature stirring pickling water tank 2, adding pure water with the addition amount of about 3/5 of the volume of the water tank, starting the water tank for stirring, adding the pickling stock solution into the water tank until the pH value of the solution is about 3.5, starting the water tank for heating, keeping the pickling solution constant temperature to 50 ℃, starting the water circulation pump 3, filling the pickling liquid into the whole hollow copper wire, raising the pressure of an air compressor 4 to 0.8MPa, setting the air-water pulse period of a pulse frequency regulator 5 to 2s, starting pulse-flexible circulation pickling, intermittently collecting a pickling liquid sample to determine the copper ion content, and taking the pickling liquid sample as a pulse-flexible circulation pickling ending index basically stably; after the pickling is finished, the pickling waste liquid in the generator hollow copper wire 7 is collected through a waste liquid water tank 9.
S3, washing with pure water: the pure water tank 8, the water circulation pump 3, the generator hollow copper wire 7 after pickling and the waste liquid tank 9 are communicated through pipelines and related valves, pure water is added into the pure water tank, the water circulation pump 3 is started, pure water flushing is started, the effluent reaches neutrality as an index of the end of pure water flushing, and flushing waste water is collected through the waste liquid tank 9.
S4, pulse air sweeping-vacuumizing drying: the air compressor 4, the pulse frequency regulator 5, the vacuum dryer 6 and the generator hollow copper wire 7 after water flushing are communicated through pipelines and related valves, the pressure of the air compressor 4 is increased to 0.8MPa, the air-water pulse period of the pulse frequency regulator 5 is set to be 2s, pulse air sweeping is started, no obvious accumulated water at the outlet of the copper wire is used as an ending index of the pulse air sweeping, the vacuum dryer 6 is started, and the hollow copper wire is vacuumized and dried.
S5, disposing acid washing waste liquid: and (3) regulating the pH value of the pickling waste liquid in the waste liquid water tank 9 to be neutral by using NaOH solution, and directly discharging the supernatant of the waste liquid into a domestic waste water biochemical treatment system of the power plant.
Example 3
If the running state of the internal cooling water system of the generator shows that the system has serious corrosion and blockage, the hollow copper conductor corrosion product is subjected to pulse-flexible acid washing by adopting relatively low-frequency pulse, and the method comprises the following steps of:
s1, pre-flushing with pure water: and (3) carrying out variable flow flushing on the corroded hollow copper wire of the generator by using pure water until the effluent is clear.
S2, pulse-flexible pickling: the method comprises the steps of connecting a pickling stock solution water tank 1, a constant-temperature stirring pickling water tank 2, a water circulation pump 3, a pre-rinsed generator hollow copper wire 7 and a waste liquid water tank 9 through pipelines and related valves, adding flexible chemical pickling liquid into the pickling stock solution water tank 1, adding a proper amount of desalted water into the constant-temperature stirring pickling water tank 2, adding pure water with the addition amount of about 3/5 of the volume of the water tank, starting the water tank for stirring, adding the pickling stock solution into the water tank until the pH value of the solution is about 3.5, starting the water tank for heating, keeping the pickling solution constant temperature to 50 ℃, starting the water circulation pump 3, filling the pickling liquid into the whole hollow copper wire, raising the pressure of an air compressor 4 to 0.8MPa, setting the air-water pulse period of a pulse frequency regulator 5 to 10s, starting pulse-flexible circulation pickling, intermittently collecting a pickling liquid sample to determine the copper ion content, taking the pickling liquid sample as a pulse-flexible circulation pickling end index basically, and collecting the waste liquid through the waste liquid water tank 9.
S3, washing with pure water: the pure water tank 8, the water circulation pump 3, the generator hollow copper wire 7 after pickling and the waste liquid tank 9 are communicated through pipelines and related valves, pure water is added into the pure water tank, the water circulation pump 3 is started, pure water flushing is started, the effluent reaches neutrality as an index of the end of pure water flushing, and flushing waste water is collected through the waste liquid tank 9.
S4, pulse air sweeping-vacuumizing drying: the air compressor 4, the pulse frequency regulator 5, the vacuum dryer 6 and the generator hollow copper wire 7 after water flushing are communicated through pipelines and related valves, the pressure of the air compressor 4 is increased to 0.8MPa, the air-water pulse period of the pulse frequency regulator 5 is set to be 2s, pulse air sweeping is started, no obvious accumulated water at the outlet of the copper wire is used as an ending index of the pulse air sweeping, the vacuum dryer 6 is started, and the hollow copper wire is vacuumized and dried.
S5, disposing acid washing waste liquid: and (3) regulating the pH value of the pickling waste liquid in the waste liquid water tank 9 to be neutral by using NaOH solution, and directly discharging the supernatant of the waste liquid into a domestic waste water biochemical treatment system of the power plant.
Example 4
If the running state of the internal cooling water system of the generator shows that the system has signs of corrosion and blockage, but is slight, in view of the fact that the internal cooling water is in a maintenance period, in order to avoid copper oxide accumulation and provide a clean copper surface for self-passivating the inner surface of the hollow copper wire, pulse-flexible acid washing is carried out on corrosion products of the hollow copper wire by adopting low-frequency pulses, and the method comprises the following steps of:
s1, pre-flushing with pure water: and (3) carrying out variable flow flushing on the corroded hollow copper wire of the generator by using pure water until the effluent is clear.
S2, pulse-flexible pickling: the method comprises the steps of connecting a pickling stock solution water tank 1, a constant-temperature stirring pickling water tank 2, a water circulation pump 3, a pre-rinsed generator hollow copper wire 7 and a waste liquid water tank 9 through pipelines and related valves, adding flexible chemical pickling liquid into the pickling stock solution water tank 1, adding a proper amount of desalted water into the constant-temperature stirring pickling water tank 2, adding pure water with the addition amount of about 3/5 of the water tank volume, starting the water tank for stirring, adding the pickling stock solution into the water tank until the pH value of the solution is about 3.5, starting the water tank for heating, keeping the pickling solution constant temperature to 50 ℃, starting the water circulation pump 3, filling the pickling liquid into the whole hollow copper wire, raising the pressure of an air compressor 4 to 0.8MPa, setting the air-water pulse period of a pulse frequency regulator 5 to 60s, starting pulse-flexible circulation pickling, intermittently collecting a pickling liquid sample to determine the copper ion content, taking the pickling liquid sample as a pulse-flexible circulation pickling end index basically, and collecting the waste liquid through the waste liquid water tank 9.
S3, washing with pure water: the pure water tank 8, the water circulation pump 3, the generator hollow copper wire 7 after pickling and the waste liquid tank 9 are communicated through pipelines and related valves, pure water is added into the pure water tank, the water circulation pump 3 is started, pure water flushing is started, the effluent reaches neutrality as an index of the end of pure water flushing, and flushing waste water is collected through the waste liquid tank 9.
S4, pulse air sweeping-vacuumizing drying: the air compressor 4, the pulse frequency regulator 5, the vacuum dryer 6 and the generator hollow copper wire 7 after water flushing are communicated through pipelines and related valves, the pressure of the air compressor 4 is increased to 0.8MPa, the air-water pulse period of the pulse frequency regulator 5 is set to be 2s, pulse air sweeping is started, no obvious accumulated water at the outlet of the copper wire is used as an ending index of the pulse air sweeping, the vacuum dryer 6 is started, and the hollow copper wire is vacuumized and dried.
S5, disposing acid washing waste liquid: and (3) regulating the pH value of the pickling waste liquid in the waste liquid water tank 9 to be neutral by using NaOH solution, and directly discharging the supernatant of the waste liquid into a domestic waste water biochemical treatment system of the power plant.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (9)
1. A pulse-flexible pickling method for a generator hollow copper conductor corrosion product is characterized by comprising the following steps of:
the pickling method comprises a pulse-flexible pickling system, wherein the system comprises a pickling stock solution tank, a constant-temperature stirring pickling tank, a water circulating pump, a pulse device, a generator hollow copper wire, a pure water tank and a waste liquid tank;
the pickling stock solution water tank is communicated to a first inlet of the constant-temperature stirring pickling water tank; the outlet of the constant-temperature stirring pickling water tank is sequentially connected with a water circulation pump and a generator hollow copper wire, and then is communicated to the second inlet of the constant-temperature stirring pickling water tank through a pipeline to form circulation; a pulse device and a vacuum dryer are sequentially connected to a pipeline between the water circulating pump and the generator hollow copper wire; the pulse device comprises an air compressor and a pulse frequency regulator;
the water circulation pump is also connected to the pure water tank;
the hollow copper conductor outlet pipeline of the generator is communicated to the waste liquid water tank through a branch;
under the condition of not adding a copper substrate corrosion inhibitor, the method utilizes a low-acidity pickling solution to couple gas-water pulse to enhance the pickling solution to carry out flexible pickling on the corrosion product of the hollow copper conductor of the generator;
the method comprises the following steps:
s1, pre-flushing pure water;
s2, pulse-flexible pickling: the pickling stock solution tank, the constant-temperature stirring pickling tank, the water circulating pump, the pre-rinsed generator hollow copper wire and the waste liquid tank are communicated through a valve; the pH value of the solution in the constant-temperature stirring pickling water tank is 3.5 by adding flexible acid liquor, and the temperature is kept; starting a water circulation pump to enable the pickling solution to be filled in the whole hollow copper wire; setting a gas-water pulse period according to the corrosion and blockage condition of a copper wire, starting an air compressor and a pulse device, carrying out pulse-flexible circulation pickling, intermittently collecting a pickling liquid sample to determine the copper ion content in the pickling liquid sample, taking the stability of the pickling liquid sample as an index of ending the pulse-flexible circulation pickling, and collecting pickling waste liquid from a waste liquid tank after the pickling is ended;
s3, washing with pure water: the pure water tank, the water circulating pump, the generator hollow copper wire after pickling and the waste liquid tank are communicated through valves; starting a water circulation pump, starting pure water flushing, taking the water outlet of the pure water circulation pump as a pure water flushing ending index, and collecting flushing wastewater by a waste liquid tank;
s4, pulse air sweeping-vacuumizing drying: the pulse device, the vacuum dryer and the generator hollow copper wire after water flushing are communicated through a valve; setting a gas-water pulse period of a pulse frequency regulator, starting pulse gas sweep, taking no obvious accumulated water at an outlet of a copper wire as an ending index of the pulse gas sweep, starting a vacuum dryer, and vacuumizing and drying an empty copper wire;
s5, disposing acid washing waste liquid: and regulating the pH value of the pickling waste liquid in the waste liquid water tank to be neutral by using NaOH solution, and directly discharging the supernatant of the waste liquid into a domestic waste water biochemical treatment system of the power plant.
2. The method according to claim 1, characterized in that: the pickling stock solution tank is filled with flexible acid liquor.
3. The method according to claim 2, characterized in that: the effective component of the flexible acid liquor is mixed organic acid consisting of ethylenediamine tetraacetic acid, citric acid and sulfamic acid.
4. The method according to claim 1, characterized in that: the air compressor is connected with the pulse frequency regulator and then connected to the pipeline.
5. The method according to claim 1, characterized in that: valves are arranged between the water circulation pump and the outlet of the constant-temperature stirring pickling water tank and between the water circulation pump and the pure water tank; a valve is arranged between the pulse device and the vacuum dryer.
6. The method according to claim 1, characterized in that: a valve and a pickling liquid sampling valve are arranged on a pipeline between the generator hollow copper wire and the constant-temperature stirring pickling water tank; and a valve is arranged on a pipeline between the generator hollow copper wire and the waste liquid water tank.
7. The pickling method according to claim 1, characterized in that: in the step S1, pure water is utilized to perform variable flow flushing on the corroded hollow copper wire of the generator until effluent is clear.
8. The pickling method according to claim 1, characterized in that: in the steps S1 and S4, the pressure of the air compressor is 0.8MPa.
9. The pickling method according to claim 1, characterized in that: in the step S4, the air-water pulse period of the pulse frequency regulator is 2S.
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| CN110160392A (en) * | 2019-05-29 | 2019-08-23 | 佛山市海天（江苏）调味食品有限公司 | A kind of on-line cleaning method of plate heat exchanger |
| WO2022005696A1 (en) * | 2020-07-03 | 2022-01-06 | Applied Materials, Inc. | Methods for refurbishing aerospace components |
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