CN104313602A - Water electrolysis pole plate surface processing method with protective film forming on surface of pole plate - Google Patents

Water electrolysis pole plate surface processing method with protective film forming on surface of pole plate Download PDF

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CN104313602A
CN104313602A CN201410673616.5A CN201410673616A CN104313602A CN 104313602 A CN104313602 A CN 104313602A CN 201410673616 A CN201410673616 A CN 201410673616A CN 104313602 A CN104313602 A CN 104313602A
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pole plate
solution
board surface
polar board
temperature
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CN104313602B (en
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State Grid Corp of China SGCC
Anyang Power Supply Co of State Grid Henan Electric Power Co Ltd
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Abstract

The invention relates to a water electrolysis pole plate surface processing method. The method comprises the specific steps that A, the surface of a pole plate made of carbon steel is cleaned; B, the pole plate is soaked in an acid corrosion solution with the temperature of 55 DEG C for 8 min, wherein the acid corrosion solution comprises, by weight, 15% of nitric acid, 3% of oxalic acid, and the balance water; C, the pole plate is soaked in a copper ion solution with the temperature of 40 DEG C for 5 min; D, the pole plate is soaked in an alkali corrosion solution with the temperature of 40 DEG C for 8 min; E, the pole pate is placed in a strong acid solution with the room temperature to be stirred, and impurities on the surface of the pole plate are removed; F, the pole plate is soaked in a conditioning fluid with the temperature of 35 DEG C for 12 min, the pole plate is flushed with clean water and dried after being taken out, and an anti-corrosion protective film is formed on the surface of the pole plate.

Description

The water electrolysis polar board surface treatment process of protective membrane can be formed at polar board surface
The application is divisional application, the invention and created name of original application: water electrolysis polar board surface treatment process, application number: 201210538399.X, the applying date: 2012-12-13 .
Technical field
The present invention relates to a kind of surface to carbon steel pole plate and carry out corrosion treatment and the processing method forming protective membrane, belong to field of metal surface treatment technology.
Background technology
Water electrolysis makes water decomposite hydrogen or oxygen under galvanic effect.In a whole set of water electrolysis equipment, electrolyzer is one of its most crucial device.Industrial conventional water electrolyzer regularly to be laminated to up to a hundred electrolytic chamber by dozens of as required and forms.Each electrolytic chamber is made up of positive plate, oxygen catalysis electrode, choke barrier film, insulated enclosure pad, hydrogen catalysis electrode, negative plate etc.Positive plate and negative plate adopt carbon steel steel plate to make usually.
Due to Strong acidic electrolyte composition electrolytic solution to metal, there is strong corrodibility, so the electrolytic solution of electrolyzer generally adopt concentration be 25% to 30% potassium hydroxide or sodium hydroxide solution.Under the effect of electric field, potassium ion or sodium ion move to negative pole, and hydroxide ion moves to positive pole, thus separate out hydrogen and oxygen.In order to reduce overpotential, reduce power consumption, the working temperature of electrolyzer is generally 85 DEG C to 90 DEG C.Such alkali concn and temperature very easily cause alkaline etching to carbon steel steel plate, so antianode plate and negative plate must carry out rotproofing.Because the caustic corrosion resistance performance of pure nickel is very excellent, at present, water electrolysis industry adopts the cathode-anode plate of carbon steel steel plate as water electrolyzer of nickel plating usually.
According to result of study display, due to nickel plating carbon steel pole plate in fact and can not plated nickel dam fully coated, nickel layer inevitably has micropore.When pole plate is in the electrolytic solution of harmful ion formation, these harmful ions can enter in the micropore of nickel layer, and enrichment in micropore, with iron ion generation hydrolysis reaction, form the acid that corrodibility is extremely strong, continue to corrode pole plate.In addition, because nickel layer is a kind of coating of cathodic, the standard potential of nickel is-0.25V, and the standard potential of iron is-0.44V, and nickel layer and plain steel can form a pair galvanic couple, electrochemical reaction will occur in the electrolytic solution when they expose simultaneously.Iron in micropore is anode, loses electronics and is dissolved; Nickel is outside negative electrode, obtains electronics, and water electrolysis is released hydrogen.It can thus be appreciated that the possibility that the nickel plating carbon steel pole plate adopting general technology to make is corroded is very big.Once pole plate occurs that serious corrosion can cause hydrogen or oxygen gas to be gone here and there mutually, leak alkali and electrical short, probably set off an explosion, threaten the safety of personnel and equipment.
Summary of the invention
The technical problem to be solved in the present invention is, proposes a kind of surface to carbon steel pole plate and carries out corrosion treatment and form protective membrane, effectively can improve the water electrolysis polar board surface treatment process of the erosion resistance after pole plate nickel plating.
The present invention is the technical scheme solving the problems of the technologies described above proposition: a kind of water electrolysis polar board surface treatment process, comprises the following steps:
A. the polar board surface of carbon steel material is cleaned;
B. pole plate is immersed in 5min to 15min in acid etching solution, carries out acid corrosion to polar board surface, the composition of described acid etching solution is the oxalic acid of the nitric acid of 8wt% to 15wt%, 2wt% to 8wt%, and all the other are water;
C. pole plate is immersed in 3min to 8min in copper ion solution, iron and cupric ion generation replacement(metathesis)reaction;
D. pole plate is immersed in 5min to 15min in caustic corrosion solution, carries out caustic corrosion to polar board surface, described caustic corrosion solution is mixed by the sodium hydroxide solution of 10g/L to 30g/L and the sodium nitrate solution of 10g/L to 30g/L;
E. pole plate is put into the strong acid solution that concentration is more than or equal to 30%, remove the impurity of polar board surface;
F. pole plate is immersed in 10min to 20min in treatment solution, protective membrane is formed at polar board surface, the composition of described treatment solution is the complexon I of 5wt% to 12wt%, the complexing agent of 0.5wt% to 3wt%, the inhibiter of 0.2wt% to 2wt%, the tensio-active agent of 0.1wt% to 0.5wt, the pH adjusting agent of 0.02wt% to 2wt%, all the other are water; The pH value of described treatment solution is 3 to 6.
Above-mentioned complexing agent is one or more in Trisodium Citrate, Sodium.alpha.-hydroxypropionate, sodium malate.
Above-mentioned inhibiter is one or more in benzotriazole, potassiumiodide, Methylbenzotriazole.
Above-mentioned tensio-active agent is one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or n-octyl sodium sulfate.
Above-mentioned pH adjusting agent is one or both in trolamine, triethylamine.
Above-mentioned copper ion solution is copper-bath or the Cupric Chloride Solution of 150mg/L to 500mg/L.
Above-mentioned strong acid solution to be temperature be 25 DEG C to 50 DEG C salpeter solution, hydrochloric acid soln or sulphuric acid soln.
The temperature of above-mentioned acid etching solution is 40 DEG C to 60 DEG C, and the temperature of described copper ion solution is 30 DEG C to 45 DEG C, and the temperature of described caustic corrosion solution is 30 DEG C to 45 DEG C.
The temperature of above-mentioned treatment solution is 25 DEG C to 45 DEG C, rinses and dry after pole plate takes out from treatment solution with clear water, and bake out temperature is 80 DEG C to 150 DEG C.
The present invention has positive effect: water electrolysis polar board surface treatment process of the present invention first carries out corrosion treatment to pole plate; protective membrane is formed again at polar board surface; corrosion treatment makes the micropore that the Surface Creation of pole plate is tiny; surface becomes coarse, is conducive to protective membrane and is compounded in better on pole plate.During corrosion treatment; first carry out acid attack and generate micropore at polar board surface; carry out alkaline corrosion again and generate more tiny micropore in polar board surface and micropore; thus make micropore be positioned at the position of more deep layer; the partial alkaline corrosive effect that replacement(metathesis)reaction occurs is more weak; thus the distribution of micropore is disperseed more, be conducive to increasing roughness, improve the composite effect of protective membrane.Treatment solution, using complexon I as main component, using complexing agent, inhibiter, tensio-active agent as ancillary component, can form fine and close protective membrane on the surface of pole plate, effectively isolate iron and contact with nickel layer, effectively promote the erosion resistance of pole plate.Complexon I does two by three carboxyls by respective oxygen and nitrogen can form complex compound with iron ion coordinating to four-coordination, and sequestering power is extremely strong; Add the erosion resistance that complexing agent and inhibiter can improve protective membrane further, add the surface tension that tensio-active agent can significantly improve protective membrane and make pole plate protective membrane finer and close.Do not adopt passivator in treatment solution of the present invention, adopt complexing agent, inhibiter with exceeding, but the complexon I that a large amount of employing is with low cost, under the prerequisite ensureing quality of forming film, greatly can reduce production cost, be with a wide range of applications.
Embodiment
Embodiment 1
The water electrolysis polar board surface treatment process of the present embodiment, concrete steps are as follows:
A. the polar board surface of carbon steel material is cleaned: successively through oil removing, washing, pickling process, will the removing such as greasy dirt, dust, corrosion of polar board surface be attached to.
B. acid corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 10min in the acid etching solution of 60 DEG C, polar board surface is tentatively corroded, forms small pit, and the diameter of pit is less than 10 μm.The composition of described acid etching solution is the oxalic acid of the nitric acid of 10wt%, 5wt%, and all the other are water.
C. ion exchange process is carried out to polar board surface.Pole plate being immersed in temperature is 5min in the copper ion solution of 40 DEG C, makes the part iron in polar board surface and pit and cupric ion generation replacement(metathesis)reaction, separates out copper.Described copper ion solution is the copper-bath of 250mg/L.
D. caustic corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 10min in the caustic corrosion solution of 30 DEG C, makes to form more more tiny pits in polar board surface and pit.Described caustic corrosion solution is mixed by the sodium hydroxide solution of 20g/L and the sodium nitrate solution of 20g/L.
E. de-sludging process is carried out to polar board surface.Strong acid solution pole plate being put into normal temperature stirs, and removes the impurity of polar board surface, then rinses with clear water.Described strong acid solution to be concentration be 30% salpeter solution.
F. pole plate is immersed 15min in the treatment solution of 40 DEG C, rinse and dry after taking-up with clear water, bake out temperature is 90 DEG C.Polar board surface forms corrosion-resisting protective film.The composition of described treatment solution is: the complexon I of 10wt%, the Trisodium Citrate of 3wt%, the benzotriazole of 1wt%, the sodium lauryl sulphate of 0.3wt%, and all the other are water, is 3 by trolamine adjust ph.
Embodiment 2
The water electrolysis polar board surface treatment process of the present embodiment, concrete steps are as follows:
A. the polar board surface of carbon steel material is cleaned: successively through oil removing, washing, pickling process, will the removing such as greasy dirt, dust, corrosion of polar board surface be attached to.
B. acid corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 15min in the acid etching solution of 50 DEG C.The composition of described pre-etching solution is the oxalic acid of the nitric acid of 8wt%, 8wt%, and all the other are water.
C. ion exchange process is carried out to polar board surface.Pole plate being immersed in temperature is 8min in the copper ion solution of 40 DEG C, makes the part iron in polar board surface and pit and cupric ion generation replacement(metathesis)reaction, separates out copper.Described copper ion solution is the copper-bath of 200mg/L.
D. caustic corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 5min in the caustic corrosion solution of 35 DEG C, makes to form more more tiny pits in polar board surface and pit.Described caustic corrosion solution is mixed by the sodium hydroxide solution of 10g/L and the sodium nitrate solution of 30g/L.
E. de-sludging process is carried out to polar board surface.Pole plate being put into temperature is that the strong acid solution of 40 DEG C stirs, and removes the impurity of polar board surface, then rinses with clear water.Described strong acid solution to be concentration be 40% hydrochloric acid soln.
F. pole plate is immersed 20min in the treatment solution of 25 DEG C, rinse and dry after taking-up with clear water, bake out temperature is 80 DEG C.Polar board surface forms corrosion-resisting protective film.The composition of described treatment solution is: the complexon I of 8wt%, the Sodium.alpha.-hydroxypropionate of 1wt%, the potassiumiodide of 0.5wt%, the Sodium dodecylbenzene sulfonate of 0.2wt%, and all the other are water, is 4.5 by triethylamine adjust ph.
Embodiment 3
The water electrolysis polar board surface treatment process of the present embodiment, concrete steps are as follows:
A. the polar board surface of carbon steel material is cleaned: successively through oil removing, washing, pickling process, will the removing such as greasy dirt, dust, corrosion of polar board surface be attached to.
B. acid corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 8min in the acid etching solution of 55 DEG C.The composition of described pre-etching solution is the oxalic acid of the nitric acid of 15wt%, 3wt%, and all the other are water.
C. ion exchange process is carried out to polar board surface.Pole plate being immersed in temperature is 5min in the copper ion solution of 40 DEG C, makes the part iron in polar board surface and pit and cupric ion generation replacement(metathesis)reaction, separates out copper.Described solion is the Cupric Chloride Solution of 300mg/L.
D. caustic corrosion process is carried out to polar board surface.Pole plate being immersed in temperature is 8min in the caustic corrosion solution of 40 DEG C, makes to form more more tiny pits in polar board surface and pit.Described caustic corrosion solution is mixed by the sodium hydroxide solution of 30g/L and the sodium nitrate solution of 15g/L.
E. de-sludging process is carried out to polar board surface.Strong acid solution pole plate being put into normal temperature stirs, and removes the impurity of polar board surface, then rinses with clear water.Described strong acid solution to be concentration be 40% salpeter solution.
F. pole plate is immersed 12min in the treatment solution of 35 DEG C, rinse and dry after taking-up with clear water, bake out temperature is 120 DEG C.Polar board surface forms corrosion-resisting protective film.The composition of described treatment solution is: the complexon I of 12wt%, the sodium malate of 2wt%, the Methylbenzotriazole of 0.5wt%, the n-octyl sodium sulfate of 0.2wt%, and all the other are water, is 4 by trolamine adjust ph.
Adopt common process to carry out nickel plating to the pole plate of the water electrolysis polar board surface treatment process through embodiment 1 to 3, then carry out SaltSprayTest.Sample is put into salt-spray cabinet, and adopt the NaCl solution of 5%, humidity is 70%, and temperature is 50 DEG C, and continue spraying 8h every day, continuous 10 days, polar board surface was without obvious corrosion phenomenon.

Claims (1)

1. a water electrolysis polar board surface treatment process, comprises step as follows:
A. the polar board surface of carbon steel material is cleaned;
B. pole plate being immersed in temperature is 8min in the acid etching solution of 55 DEG C; The composition of described pre-etching solution is the oxalic acid of the nitric acid of 15wt%, 3wt%, and all the other are water;
C. pole plate being immersed in temperature is 5min in the copper ion solution of 40 DEG C, makes the part iron in polar board surface and pit and cupric ion generation replacement(metathesis)reaction, separates out copper;
D. pole plate being immersed in temperature is 8min in the caustic corrosion solution of 40 DEG C, carries out caustic corrosion to polar board surface; Described caustic corrosion solution is mixed by the sodium hydroxide solution of 30g/L and the sodium nitrate solution of 15g/L;
E. strong acid solution pole plate being put into normal temperature stirs, and removes the impurity of polar board surface, then rinses with clear water; Described strong acid solution to be concentration be 40% salpeter solution;
F. pole plate is immersed 12min in the treatment solution of 35 DEG C, rinse and dry after taking-up with clear water, polar board surface forms corrosion-resisting protective film; The composition of described treatment solution is: the complexon I of 12wt%, the sodium malate of 2wt%, the Methylbenzotriazole of 0.5wt%, the n-octyl sodium sulfate of 0.2wt%, and all the other are water, is 4 by trolamine adjust ph.
CN201410673616.5A 2012-12-13 2012-12-13 The water electrolysis polar board surface processing method of diaphragm can be formed at polar board surface Expired - Fee Related CN104313602B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61276982A (en) * 1985-05-30 1986-12-06 Nec Corp Plating method for magnesium alloy
JPH06116734A (en) * 1992-10-02 1994-04-26 Mitsui Mining & Smelting Co Ltd Highly corrosion resistant coating method of magnesium-base alloy
CN1712573A (en) * 2004-06-24 2005-12-28 侯文清 Surface cladding treatment of ferro-manganese aluminium alloy
CN1793425A (en) * 2005-12-30 2006-06-28 东北大学 Process for compound surface sheilding of metal magnesium and magnesium alloy
CN102021552A (en) * 2009-09-21 2011-04-20 邵阳市创捷化工有限公司 Modifier for black metal surface matrix and production method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61276982A (en) * 1985-05-30 1986-12-06 Nec Corp Plating method for magnesium alloy
JPH06116734A (en) * 1992-10-02 1994-04-26 Mitsui Mining & Smelting Co Ltd Highly corrosion resistant coating method of magnesium-base alloy
CN1712573A (en) * 2004-06-24 2005-12-28 侯文清 Surface cladding treatment of ferro-manganese aluminium alloy
CN1793425A (en) * 2005-12-30 2006-06-28 东北大学 Process for compound surface sheilding of metal magnesium and magnesium alloy
CN102021552A (en) * 2009-09-21 2011-04-20 邵阳市创捷化工有限公司 Modifier for black metal surface matrix and production method thereof

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Inventor after: Gao Xiaogang

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