CN105238116B - A kind of electric generator inner cooling water tubular copper conductor corrosion protective layers and preparation method thereof - Google Patents
A kind of electric generator inner cooling water tubular copper conductor corrosion protective layers and preparation method thereof Download PDFInfo
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- CN105238116B CN105238116B CN201510604652.0A CN201510604652A CN105238116B CN 105238116 B CN105238116 B CN 105238116B CN 201510604652 A CN201510604652 A CN 201510604652A CN 105238116 B CN105238116 B CN 105238116B
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- copper conductor
- protective layers
- tubular copper
- corrosion protective
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 78
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 239000004020 conductor Substances 0.000 title claims abstract description 65
- 230000007797 corrosion Effects 0.000 title claims abstract description 55
- 238000005260 corrosion Methods 0.000 title claims abstract description 55
- 239000011241 protective layer Substances 0.000 title claims abstract description 33
- 239000000498 cooling water Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000002989 phenols Chemical class 0.000 claims abstract description 19
- 229920006254 polymer film Polymers 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- -1 diphenol compound Chemical class 0.000 claims description 13
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229920000768 polyamine Chemical class 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical group OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012224 working solution Substances 0.000 claims description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000005487 catechin Nutrition 0.000 claims description 3
- 229950001002 cianidanol Drugs 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 2
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 claims description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical class NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 claims 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- XMOCLSLCDHWDHP-UHFFFAOYSA-N L-Epigallocatechin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C1=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-UHFFFAOYSA-N 0.000 claims 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 claims 1
- 238000000280 densification Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 description 2
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000656 polylysine Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940030275 epigallocatechin gallate Drugs 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Abstract
The invention discloses a kind of electric generator inner cooling water tubular copper conductor corrosion protective layers and preparation method thereof, tubular copper conductor corrosion protective layers are in the hollow by the alkaline solution injection tubular copper conductor containing phenolic compound and aminated compounds, by reacting generation polymer between phenolic compound and aminated compounds and being deposited on the polymer film that tubular copper conductor hollow inner surface is formed：The polymer film densification, good stability, it can effectively suppress the copper corrosion of tubular copper conductor hollow inner surface, and the preparation method of corrosion protective layers is simple, low cost, compared to prior art, small mixed bed, alkali lye Dropping feeder in water- cooling generator can be omitted, and effectively reduce investment and operation expense.
Description
Technical field
The present invention relates to a kind of electric generator inner cooling water tubular copper conductor corrosion protective layers and preparation method thereof；Belong to motor work
Journey technical field.
Background technology
The stator of the stator winding of the high-rating generators such as nuclear power plant, thermal power plant and hydroelectric power plant and large-scale pair of water-cooled generator,
Rotor windings are generally cooled down using water in tubular copper conductor inner loop, for reducing generator bar temperature.However, hollow copper
Wire is easily corroded by inner cold water, causes electrical conductivity to increase, insulation degree reduction, leakage current increase；Corrosion product is also possible to
Wire is blocked, causes local overheating even motor damage, causes compressor emergency shutdown accident, cause serious economic loss.To ensure
The safety and economic operation of generator, it is necessary to take certain measure to reduce or prevent that tubular copper conductor from corroding.
Addition corrosion inhibiter and control water quality are the common methods of control and the tubular copper conductor corrosion of reduction electric generator inner cooling water.
Corrosion inhibiter typically selects nitrogenous azole, amine, pyridines and derivative corrosion inhibiter.But, corrosion inhibiter solubility in water
It is smaller, cosolvent need to be added, and easily precipitated with copper ion complexing generation, cause tubular copper conductor to block overtemperature, institute exists in this way
It is less in practical application.It is a kind of method quickly grown in recent years to control inner cold water water quality, and its cardinal principle purifies water
And alkalescence is adjusted to, copper conductor is in passivation water quality, surface forms passivation protection film, prevent that impurities in water from corroding copper and leading
Line.However, the method need to often change resin, and specific equipment need to be used to carry out precise control to water quality, it is less economical.And
And, passivation protection film is simultaneously unstable, and water quality is very easy to be destroyed once occurring fluctuation, and unit operation operating mode is mutated or is
System slightly defect may destroy diaphragm, and Water-quality control is slightly not in place to be possible to can occur heavy corrosion.
The content of the invention
Electric generator inner cooling water tubular copper conductor corrosion protection requirement, less economical, control can not be met for prior art
Complicated the problem of, it is to provide a kind of densification, good stability, can effectively suppress in tubular copper conductor hollow that the purpose of the present invention, which is,
The corrosion protective layers of portion surface copper corrosion.
It is to provide a kind of simple to operate, inexpensive to prepare the tubular copper conductor and corrode that another object of the present invention, which is,
The method of overcoat.
In order to realize the technical purpose of the present invention, the invention provides a kind of corrosion of electric generator inner cooling water tubular copper conductor is anti-
Sheath, the corrosion protective layers are that the hollow of tubular copper conductor is injected by the alkaline solution containing phenolic compound and aminated compounds
In, by reacting generation polymer between phenolic compound and aminated compounds and being deposited on tubular copper conductor hollow inner surface shape
Into polymer film：Wherein, the mass percent of phenolic compound and aminated compounds is 40~95%:5~60%；It is described
Phenolic compound be diphenol and/or polyphenolic substance；Described aminated compounds is diamines and/or polyamine compounds.
Technical scheme passes through chemical reaction using diphenol or Polyphenols with diamines or polyamine compounds first
In one layer of densification of tubular copper conductor hollow inner surface formation, the polymer membrane layer of stable chemical nature, this one polymer
Film can effectively separate tubular copper conductor hollow inner surface and directly be contacted with outside, play a part of preventing copper corrosion.In addition, amine
The remaining amido of class compound can make tubular copper conductor surface microenvironment keep alkalescence, further suppress copper corrosion；And phenol
Class compound can form strong Coordinative Chemistry key with copper conductor surface, strengthen the Interface adhesive strength of overcoat, while unreacted
Complete phenols prevents the oxygen corrosion of polymer and tubular copper conductor as antioxidant.
It is preferred that scheme in, the mass percent of phenolic compound and aminated compounds is 43~85%:15~57%.
It is preferred that scheme in, diphenol compound be hydroquinones, resorcinol and catechol at least one.
It is preferred that scheme in, polyphenolic substance be gallic acid, tannin, catechin, L-Epicatechin gallate and table
At least one in nutgall catechin gallic acid ester.
It is preferred that scheme in, diamine compound be ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, p-phenylenediamine,
M-phenylene diamine (MPD), 1,2- diamines butylcyclohexane, 1,3- diamines butylcyclohexane, 1,4- diamines butylcyclohexane, 3,5- diaminobenzoic acids
With at least one in lysine.
It is preferred that scheme in, polyamine compounds be equal benzene triamine, 1,2,4- tri- amido benzene, three (2- amine ethyl) amine, diethyl
Alkene triamine, triethylene tetramine, TEPA, pentaethylene hexamine, the amine of six ethene seven, polyethylene polyamine, polyvinylamine, polyethylene
At least one in imines and polylysine.
Present invention also offers the preparation method of the electric generator inner cooling water tubular copper conductor corrosion protective layers, this method is
Phenolic compound and aminated compounds are dissolved in water, and adjust pH to alkalescence, working solution is obtained；The working solution is injected into hollow
In the hollow of copper conductor, reacted at a temperature of 15~60 DEG C, in tubular copper conductor hollow inner surface formation corrosion protective layers.
It is preferred that scheme in, by hydrochloric acid and/or sodium hydroxide solution adjustment work liquid, its pH value is maintained 8~13
In the range of；Preferably pH value is maintained in the range of 8.5~11；Most preferably 9~10.5.The concentration of hydrochloric acid is preferably 1mol/L；
The concentration of NaOH solution is preferably 1mol/L.
It is preferred that scheme in, in working solution the gross mass degree of phenolic compound and aminated compounds be 0.1~
5%；Preferably 0.2~3.7%；Most preferably 0.5~1.8%.
It is preferred that scheme in, the time reacted at a temperature of 15 DEG C~60 DEG C be 4~48 hours.It is preferred that reaction temperature be 20
DEG C~45 DEG C；Most preferably 25 DEG C~40 DEG C.Reaction time is preferably 6~40h, most preferably 10~36h.
Compared with the prior art, the present invention has following remarkable advantage and beneficial effect：
Technical scheme is used first, and diphenol or polyphenolic substance are used as hollow copper with diamines or polyamine compounds
Wire hollow inside corrosion overcoat raw material, diphenol or Polyphenols are with diamines or polyamine compounds by chemically reacting in sky
Core copper conductor hollow inner surface formation one layer of densification, polymer membrane of stable chemical nature, this one polymer film can have
Effect cut-off tubular copper conductor hollow inner surface is directly contacted with outside, plays a part of preventing copper corrosion.In addition, amine chemical combination
The remaining amido of thing can make tubular copper conductor surface microenvironment keep alkalescence, further suppress copper corrosion；And phenols chemical combination
Thing can form strong Coordinative Chemistry key with copper conductor hollow inner surface, strengthen the Interface adhesive strength of overcoat, while unreacted
Complete phenols prevents the oxygen corrosion of polymer and tubular copper conductor as antioxidant.
Tubular copper conductor corrosion protective layers prepared by technical scheme are to be deposited on sky by in-situ polymerization growth
Core copper conductor hollow inner surface, overcoat is uniform, fine and close；Interface adhesive strength with copper is strong, and chemical stability is good, can transport for a long time
OK, it is ensured that protection effect.In addition, the preparation method of overcoat is simple, easy to operate, overcoat need not strictly control water after being formed
Matter.Compared to prior art, small mixed bed, alkali lye Dropping feeder in water- cooling generator can be omitted, and effectively reduced investment and transported
Row maintenance cost.
Brief description of the drawings
【Fig. 1】Corrosion-free overcoat, embodiment 1, embodiment 2 prepare tubular copper conductor hollow inner surface after corrosion protective layers
Electron scanning micrograph.
【Fig. 2】The dynamic potential polarization curve and impedance spectrum of the copper sheet of corrosion-free overcoat and copper sheet after the processing of embodiment 1
Figure.
【Fig. 3】Copper sheet is passed through in desalination water running 60 days after the tubular copper conductor of corrosion-free overcoat is handled with embodiment 3
The content of copper ion of cold water.
Embodiment
Illustrate the present invention below by way of specific embodiment, but embodiment is merely to illustrate, and is not limit the scope of the invention.
In the case where not departing from above method thought range of the present invention, made according to ordinary skill knowledge and customary means
Various replacements and change, should be included in the scope of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1
(1) by 815g catechols and 185g ethylenediamines, stirring and dissolving in 199kg water is added, 1mol/L hydrochloric acid is added dropwise
It is 9.0 ± 0.5 that the aqueous solution and the 1mol/L NaOH aqueous solution, which adjust solution ph, obtains initial soln, standby, wherein adjacent benzene two
Total weight/mass percentage composition of phenol and ethylenediamine is 0.5%, and ethylenediamine accounts for the 18.5% of the gross mass of catechol and ethylenediamine.
(2) initial soln is injected in the electric generator inner cooling water tubular copper conductor rinsed well, it is 25 to keep solution temperature
± 5 DEG C, after being reacted through 36h, solution after reaction is allowed to dry, rinsed well with water, i.e., obtained in tubular copper conductor hollow inner surface
Corrosion protective layers.
Embodiment 2
(1) by 1580g pyrogallols and 420g triethylene tetramines, stirring and dissolving in 198kg water is added, is added dropwise 1mol/L's
Aqueous hydrochloric acid solution and 1mol/L NaOH aqueous solution regulation solution ph are 10.5 ± 0.5, obtain initial soln, standby, wherein
Total weight/mass percentage composition of catechol and ethylenediamine is 1.0%, and ethylenediamine accounts for the gross mass of catechol and ethylenediamine
21.0%.
(2) initial soln is injected in the electric generator inner cooling water tubular copper conductor rinsed well, it is 35 to keep solution temperature
± 5 DEG C, after being reacted through 24h, solution after reaction is allowed to dry, rinsed well with water, i.e., obtained in tubular copper conductor hollow inner surface
Corrosion protective layers.
Embodiment 3
(1) by 1940.4g tannin and 1659.6g polyethyleneimines, stirring and dissolving in 196.4kg water is added, 1mol/ is added dropwise
It is 10.0 ± 0.5 that L aqueous hydrochloric acid solution and the 1mol/L NaOH aqueous solution, which adjust solution ph, obtains initial soln, standby, its
Total weight/mass percentage composition of middle catechol and ethylenediamine is 1.8%, and ethylenediamine accounts for the gross mass of catechol and ethylenediamine
46.1%.
(2) initial soln is injected in the electric generator inner cooling water tubular copper conductor rinsed well, it is 40 to keep solution temperature
± 5 DEG C, after being reacted through 10h, solution after reaction is allowed to dry, rinsed well with water, i.e., obtained in tubular copper conductor hollow inner surface
Corrosion protective layers.
Embodiment 4
(1) by 1136.2g Epigallo-catechin gallate (EGCG)s and 1463.8g polylysines, add in 197.4kg water
Stirring and dissolving, it is 9.5 ± 0.5 that 1mol/L aqueous hydrochloric acid solution and 1mol/L NaOH aqueous solution regulation solution ph, which is added dropwise, is obtained
Initial soln is obtained, standby, wherein total weight/mass percentage composition of catechol and ethylenediamine is 1.3%, and ethylenediamine accounts for adjacent benzene two
The 56.3% of the gross mass of phenol and ethylenediamine.
(2) initial soln is injected in the electric generator inner cooling water tubular copper conductor rinsed well, it is 40 to keep solution temperature
± 5 DEG C, after being reacted through 18h, solution after reaction is allowed to dry, rinsed well with water, i.e., obtained in tubular copper conductor hollow inner surface
Corrosion protective layers.
The surface scan electricity for the corrosion protective layers that the tubular copper conductor of corrosion-free overcoat, embodiment 1 are prepared with embodiment 2
Sub- microphotograph is as shown in figure 1, (being respectively left figure, middle figure and right figure).As shown in Figure 1, prepare after corrosion protective layers, hollow
Copper conductor surface is covered with one layer of complete organic layer.
Take 1 × 1cm2Tubular copper conductor and the embodiment 3 of corrosion-free overcoat prepare the hollow copper after corrosion protective layers
Wire, with epoxy encapsulation, it (is respectively left figure and the right side to test dynamic potential polarization curve with impedance spectrum using three-electrode method
Figure), as shown in Figure 2.Being understood to prepare after corrosion protective layers by dynamic potential polarization curve figure, corrosion potential is increased to from -305mV -
242mV, corrosion current is reduced to 1.05 μ A from 3.74 μ A.Impedance spectra can be seen that face coat resistance is remarkably reinforced, explanation
Prepare after corrosion protective layers, the corrosion tendency on copper conductor surface declines, and the corrosion to copper conductor serves obvious inhibiting effect.
The tubular copper conductor (numbering 1) of corrosion-free overcoat processing, embodiment 1~4 prepare the hollow after corrosion protective layers
Copper conductor (numbering 2~5) and the micro- basification device of use control the tubular copper conductor (numbering 6) of water quality to run in 60 days,
Content of copper ion monitoring curve in inner cold water is as shown in figure 3, the untreated tubular copper conductor operation it can be seen from data in figure
No more than content of copper ion in 20 sky and water i.e. more than 20 μ g/L, professional standard DL/T801-2010 requirement is not met, and is used
Copper ion in inner cold water, which is discharged into, after the preparation corrosion protective layers of the embodiment of the present invention 1~4 is still below 8 μ g/L after being run through 60 days,
More untreated wire is decreased obviously, and fluctuating range is smaller than water quality controlling method.
Claims (8)
1. a kind of preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers, it is characterised in that：By phenolic compound
Water is dissolved in aminated compounds, and adjusts pH to alkalescence, working solution is obtained；The working solution is injected to the hollow of tubular copper conductor
In, reacted at a temperature of 15~60 DEG C, in tubular copper conductor hollow inner surface formation corrosion protective layers；
Described corrosion protective layers are injected the sky of tubular copper conductor by the alkaline solution containing phenolic compound and aminated compounds
In core, by reacting generation polymer between phenolic compound and aminated compounds and being deposited on tubular copper conductor hollow inner surface
The polymer film of formation：
Wherein, the mass percent of phenolic compound and aminated compounds is 40~95%:5~60%；Described phenols chemical combination
Thing is diphenol and/or polyphenolic substance；Described aminated compounds is diamines and/or polyamine compounds；
The gross mass degree of phenolic compound and aminated compounds is 0.1~5% in described working solution.
2. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 1, its feature exists
In：By hydrochloric acid and/or sodium hydroxide solution adjustment work liquid, its pH value is set to maintain in the range of 8~13.
3. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 1, its feature exists
In：Reaction time is 4~48 hours.
4. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 1, its feature exists
In：The mass percent of phenolic compound and aminated compounds is 43~85%:15~57%.
5. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 4, its feature exists
In：Described diphenol compound is at least one in hydroquinones, resorcinol and catechol.
6. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 4, its feature exists
In：Described polyphenolic substance is gallic acid, tannin, catechin, L-Epicatechin gallate and epigallocatechin
At least one in gallate.
7. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 4, its feature exists
In：Described diamine compound be ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, p-phenylenediamine, m-phenylene diamine (MPD), 1,
In 2- diamines butylcyclohexane, 1,3- diamines butylcyclohexane, 1,4- diamines butylcyclohexane, 3,5- diaminobenzoic acids and lysine
It is at least one.
8. the preparation method of electric generator inner cooling water tubular copper conductor corrosion protective layers according to claim 1, its feature exists
In：Described polyamine compounds are equal benzene triamine, the amido benzene of 1,2,4- tri-, three (2- amine ethyl) amine, diethylenetriamine, triethylene
Tetramine, TEPA, pentaethylene hexamine, the amine of six ethene seven, polyethylene polyamine, polyvinylamine, polyethyleneimine and poly- bad ammonia
At least one in acid.
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