CN113088981B - Preparation, treatment and regeneration method of stainless steel pickling passivation solution - Google Patents
Preparation, treatment and regeneration method of stainless steel pickling passivation solution Download PDFInfo
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- CN113088981B CN113088981B CN202110388045.0A CN202110388045A CN113088981B CN 113088981 B CN113088981 B CN 113088981B CN 202110388045 A CN202110388045 A CN 202110388045A CN 113088981 B CN113088981 B CN 113088981B
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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
- C23G1/08—Iron or steel
- C23G1/085—Iron or steel solutions containing HNO3
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/86—Regeneration of coating baths
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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
- C23G1/36—Regeneration of waste pickling liquors
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Abstract
The invention discloses a pickling passivation process of stainless steel, which comprises the following steps of: adding concentrated sulfuric acid, sulfate and chloride into water to form an original solution; preparing electrolyte by electrolyzing the raw solution: adopting a boron-doped diamond electrode as an anode material and a cathode material, electrolyzing the original solution to generate hydroxyl radicals in situ under the condition of electrifying, oxidizing sulfate ions and chloride ions of the original solution and forming strong oxidants such as persulfate, hypochlorite, perchlorate and the like; adding nitric acid, fluoride salt or hydrogen fluoride salt, alcohols, thiourea and benzoate to finally form stainless steel pickling passivation solution; and (3) soaking the stainless steel product to be treated for 10-120min, and then washing the stainless steel product with water, wherein the treated stainless steel pickling passivation solution waste liquid can be recycled after electrolysis and filtration. The process is simple, convenient to operate, environment-friendly and energy-saving.
Description
Technical Field
The invention relates to the technical field of stainless steel surface treatment, in particular to a preparation method of a stainless steel pickling passivation solution, a stainless steel pickling passivation treatment process and a regeneration method of the pickling passivation solution.
Background
Stainless steel is widely used because of its excellent corrosion resistance and good appearance. The stainless steel is inevitably subjected to heat treatment, welding, forging, casting and other processing processes in the production process, and black oxide scales are generated on the surface. The oxide skin affects not only the appearance quality of stainless steel, but also the service life of the workpiece. The main purpose of pickling is to remove the oxide film produced by high temperature operation of stainless steel and expose the original surface of stainless steel. The stainless steel oxide skin mainly comprises Ni02、Cr2O3、FeO·Cr2O3、FeO·Cr2O3、Fe203The composition of the equal compact oxides has great difficulty in acid cleaning and passivation processing, and new processes and formulas are required to be developed. Hydrochloric acid is commonly used in the traditional pickling solution, and the volatility of the hydrochloric acid is not beneficial to the stability of the pickling solution and the environmental protection. For thicker black-purple scale, treatment with concentrated alkali (such as NaOH) with strong oxidizing agent at high temperature (typically at 120-150 deg.C) is required. Therefore, the traditional pickling method has high energy consumption, and the produced sewage contains heavy metals, nitrate nitrogen, nitrite nitrogen and other substances which are difficult to remove.
Passivation after pickling is a common procedure for stainless steel surface treatment. Parts after pickling have poor corrosion resistance in air. If exposed to air, the surface of the part can rust. To enhance the corrosion resistance of the part, the surface of the part must be roughBecomes a compact passive film with good corrosion resistance, thereby achieving the purpose of corrosion resistance. Nitric acid is commonly used for treatment at present, but the nitric acid is corroded on materials made of certain materials. Therefore, pre-passivation is often performed using stronger oxidants such as potassium dichromate, sodium dichromate, chromic anhydride. However, most of these oxidants contain highly toxic carcinogenic Cr6+And the super-strong oxidant is very easy to reduce, so the super-strong oxidant is not easy to store and influences the service life of the passivation solution.
Disclosure of Invention
The invention aims to provide a stainless steel pickling passivation solution, which can finish pickling passivation treatment of stainless steel after a stainless steel product is soaked and washed, and is suitable for dense oxide scales, oil stains, iron rust and welding spots generated in the processing process of materials such as 3-series stainless steel SUS303, 304, 316L and 316 and 2-series duplex stainless steel SUS201, 202 and 204.
The specific technical scheme is as follows:
a preparation method of stainless steel pickling passivation solution comprises the following steps:
1) preparing a raw solution:
adding concentrated sulfuric acid, sulfate and chloride into water to form an original solution;
2) preparing electrolyte by electrolyzing the raw solution:
adopting an electrode anode material: one or more of boron-doped diamond, lead oxide, glassy carbon electrode and ruthenium-titanium-iridium oxide;
adopting electrode cathode materials: one or more of boron-doped diamond, lead oxide, glassy carbon electrode, ruthenium-titanium-iridium oxide, graphite, stainless steel and lead plate;
electrolyzing the raw solution prepared in the step 1), inserting the electrode anode material and the electrode cathode material into the raw solution and connecting the electrode anode material and the electrode cathode material with a power supply, wherein under the condition of electrifying, hydroxyl radicals are generated on the surface of the anode material, sulfate ions and chloride ions of the raw solution are oxidized by the strong oxidizing property of the hydroxyl radicals to form an oxidizing agent, and the oxidizing agent comprises persulfuric acid or/and persulfate, hypochlorous acid or/and hypochlorite, perchloric acid or/and perchlorate; the reaction formula is as follows:
H2O→2OH·+O2
SO4 2+OH·-→S2O8 2-+H+
Cl-+OH·→ClO-+H+
Cl-++OH·→ClO4 -+H+
3) preparing stainless steel pickling passivation solution:
adding nitric acid into the electrolyte in the step 2), adding fluoride salt or/and hydrogen fluoride salt: one or more of sodium fluoride, potassium fluoride and ammonium bifluoride, and other additives are added: alcohols, thiourea and benzoic acid to finally form the stainless steel pickling passivation solution.
Adding 2-200g of 98% concentrated sulfuric acid into each liter of water in the step 1); adding 0.1-250g of sodium sulfate or/and potassium sulfate; adding 0.1-300g of sodium chloride or/and potassium chloride.
Current density during electrolysis in step 2): 5mA/cm2-1A/cm2And time: 1-120min, voltage: 2-50V.
The electrode anode material and the electrode cathode material adopted in the step 2) are preferably boron-doped diamond.
The components of the super strong oxidant generated by electrolysis in the step 2) by weight are as follows: 0.01-10% of persulfate, 0.01-6% of hypochlorite and 0.01-1.1% of perchlorate; no chemical addition and no chromium pollution.
Adding nitric acid into each liter of electrolyte in the step 3): 2-300 g; adding fluoride salt or/and hydrogen fluoride salt: 1-20g of one or more of sodium fluoride, potassium fluoride and ammonium bifluoride; adding other additives: 0.02-20g of glycerol, 0.01-18g of diphenylthiourea or/and thiourea and 0.1-10g of sodium benzoate or/and ammonium benzoate.
The stainless steel product is treated by the prepared stainless steel pickling passivation solution: and (3) putting the stainless steel product to be treated into the stainless steel pickling passivation solution, soaking for 10-120min, and then washing with water.
The regeneration method of the stainless steel pickling passivation solution after the stainless steel product is treated comprises the following steps: after the stainless steel pickling passivation solution waste liquid after the stainless steel product is treated is electrolyzed in the step 2) and precipitates are filtered, concentrated sulfuric acid, chloride and nitric acid are added, fluoride salt or/and hydrogen fluoride salt are added, and other additives are added: alcohol, dimethyl phenylthiourea or/and thiourea, sodium benzoate and ammonium benzoate to obtain the regenerated liquid of the stainless steel pickling and passivating liquid.
In the regeneration method of the stainless steel pickling and passivating solution, 0-50g of 98% concentrated sulfuric acid, 0.1-10g of sodium chloride or/and potassium chloride, 2-150g of nitric acid, 0.1-3g of sodium fluoride or/and potassium fluoride or/and ammonium bifluoride, 0.02-10g of glycerol, 0.01-0.8g of xylenesulfenuron or/and thiourea, and 0.1-10g of sodium benzoate or/and ammonium benzoate are added into each liter of the waste liquid of the stainless steel pickling and passivating solution.
During electrolysis, part of metal ions in the waste liquid of the pickling passivation solution are as follows: cr ions, Ni ions, etc. are reduced to the cathode; in the electrolytic process, the anode material generates hydroxyl radical OH in situ, so that not only can heavy metal ions in the pickling and passivating solution waste liquid be oxidized to form precipitates, but also strong oxides such as persulfate, hypochlorite, perchlorate and the like can be synthesized again. The reaction formula is as follows:
H2O→2OH·+O2
SO4 2+OH·-→S2O8 2-+H+
Cl-+OH·→ClO-+H+
Me++OH·→Me2OX/Me(OH)X↓+H+
(Me represents one or more of Fe, Mn, Ni, Cr, V, Si, Ti and Mo)
The invention has the following advantages:
1. the pickling passivation solution prepared by the invention can be used for directly soaking stainless steel to be pickled and passivated and then washing the stainless steel with water, so that the pickling and passivation treatment of the stainless steel can be completed, the redundant steps are not needed, and the operation is quite simple and convenient;
2. the whole stainless steel pickling passivation solution and the treatment process do not contain phosphorus, yellow smoke or heavy metal chromium, and an unstable strong oxidant is not required to be added;
3. the stainless steel pickling passivation solution has stable performance and is not easy to age. After aging, the waste liquid is electrolyzed again, the bottom sediment is filtered, and then the medicament is added, so that the waste liquid can be regenerated and reused, the zero discharge of sewage is realized, and the environmental protection is facilitated;
4. the whole process can remove the scale and form a passive film without heating or special heat-resisting equipment and heating equipment, and simultaneously reduces the energy consumption cost.
The specific implementation mode is as follows:
example 1
The pickling passivation treatment process of the stainless steel product comprises the following steps:
1) preparing a raw solution:
adding 2-200g of 98% concentrated sulfuric acid into 1L of water according to the proportion; adding 0.1-250g of sodium sulfate or/and potassium sulfate; adding 0.1-300g of sodium chloride or/and potassium chloride to form a raw solution;
2) preparing electrolyte by electrolyzing the raw solution:
adopting boron-doped diamond electrode anode material and boron-doped diamond electrode cathode material, current density: 20-200mA/cm2And time: 10-40min, voltage: 2-50V; electrolyzing the raw solution prepared in the step 1), generating hydroxyl radicals through an electrode anode material, oxidizing sulfate ions and chloride ions of the raw solution through the strong oxidizing property of the hydroxyl radicals to form an oxidizing agent, wherein the oxidizing agent comprises the following components in parts by weight: 0.01-10% of persulfate, 0.01-6% of hypochlorite and 0.01-1.1% of perchlorate; the reaction formula is as follows:
H2O→2OH·+O2
SO4 2+OH·-→S2O8 2-+H+
Cl-+OH·→ClO-+H+
Cl-++OH·→ClO4 -+H+
3) preparing stainless steel pickling passivation solution:
adding nitric acid into each liter of electrolyte in the step 2): 2-300 g; adding fluoride salt or/and hydrogen fluoride salt: 1-20g of one or more of sodium fluoride, potassium fluoride and ammonium bifluoride; adding other additives: 0.02-20g of glycerol, 0.01-18g of dimethylthiourea or/and thiourea and 0.1-10g of sodium benzoate or/and ammonium benzoate, and finally forming the stainless steel pickling passivation solution.
4) The stainless steel product is treated by the prepared stainless steel pickling passivation solution: and (3) putting the stainless steel product to be treated into the stainless steel pickling passivation solution, soaking for 10-120min, and then washing with water.
5) After the stainless steel pickling passivation solution waste liquid after the stainless steel product is treated is electrolyzed in the step 2) and precipitates are filtered, according to the steps, 0-50g of 98% concentrated sulfuric acid, 0.1-10g of sodium chloride or/and potassium chloride, 2-150g of nitric acid, 0.1-3g of sodium fluoride or/and potassium fluoride or/and ammonium bifluoride, 0.02-10g of glycerol, 0.01-0.8g of xylenesulfenyl urea or/and thiourea and 0.1-10g of sodium benzoate or/and ammonium benzoate are added into each liter of the stainless steel pickling passivation solution waste liquid to obtain the regeneration liquid of the stainless steel pickling passivation solution, namely the stainless steel product can be circularly pickled and passivated in the step 4).
During electrolysis, part of metal ions in the waste liquid of the pickling passivation solution are as follows: cr ions, Ni ions, etc. are reduced to the cathode; in the electrolytic process, the anode material generates hydroxyl radical OH in situ, so that not only can heavy metal ions in the pickling and passivating solution waste liquid be oxidized to form precipitates, but also strong oxides such as persulfate, hypochlorite, perchlorate and the like can be synthesized again. The reaction formula is as follows:
H2O→2OH·+O2
SO4 2+OH·-→S2O8 2-+H+
Cl-+OH·→ClO-+H+
Me++OH·→Me2OX/Me(OH)X↓+H+
(Me represents one or more of Fe, Mn, Ni, Cr, V, Si, Ti and Mo)
Example 2
A preparation and treatment process of an SUS304 stainless steel pickling passivation solution comprises the following steps:
1) preparing a raw solution:
adding 5-50g of 98% concentrated sulfuric acid into water, and adding 50g of sodium sulfate and 50g of sodium chloride to form an original solution;
2) preparing electrolyte by electrolyzing the raw solution:
adopting boron-doped diamond electrode anode material and boron-doped diamond electrode cathode material, and current density: 20-200mA/cm2And time: 10-40min, voltage: 2-50V; electrolyzing the raw solution prepared in the step 1), generating hydroxyl radicals through an electrode anode material, oxidizing sulfate ions and chloride ions of the raw solution through the strong oxidizing property of the hydroxyl radicals to form an oxidizing agent, wherein the oxidizing agent comprises the following components in parts by weight: 0.1-3% of persulfate, 1-3% of hypochlorite and 0.1-0.3% of perchlorate. (ii) a The reaction formula is as follows:
H2O→2OH·+O2
SO4 2+OH·-→S2O8 2-+H+
Cl-+OH·→ClO-+H+
Cl-++OH·→ClO4 -+H+
3) preparing stainless steel pickling passivation solution:
adding 2-300g of nitric acid, 2-4g of sodium fluoride, 3.05-5.9g of glycerol, 0.2-0.5g of xylenesulfenuron or thiourea and 2.5-5.0g of sodium benzoate into each liter of the electrolyte in the step 2) to prepare the stainless steel pickling passivation solution.
And (3) putting the stainless steel product to be treated into the prepared stainless steel pickling passivation solution, soaking for 10-120min, and then washing with water to complete the passivation treatment of the stainless steel product.
The yellow-purple oxide skin on the upper surface of the SUS304 stainless steel workpiece after pickling and passivation is completely removed, and white metal color appears on the surface of the workpiece after passivation. And (3) passivation effect testing: NSS neutral salt spray test is carried out for 120h according to OO-P-35B requirements, the stainless steel is stainless, and the passivation performance is stable; according to titration experiment analysis of copper sulfate, no copper precipitation occurs within 5 minutes.
After 500m of accumulation2After the stainless steel workpiece is treated, the pH value of the pickling passivation solution is raised to 1-3, and the density of the pickling passivation solution is increased<1.10g/cm3It is not suitable for further treatmentThe preparation is used. Hence, the need for "regeneration";
and (3) electrolyzing the aged pickling passivation solution in the step 2), and filtering by an acid-resistant filter pump. And then adding 0-25g of 98% concentrated sulfuric acid, 10g of sodium chloride, 50g of nitric acid, 0.2-2g of sodium fluoride, 1.2-3.5g of glycerol, 0.1-0.2g of thiourea and 1.0-3.0g of sodium benzoate to obtain the regeneration liquid of the stainless steel pickling passivation solution.
And (3) placing the stainless steel product to be treated into the regenerated liquid of the prepared stainless steel pickling and passivating solution, soaking for 10-120min, and then washing with water to be clean, so that the pickling and passivating treatment of the stainless steel product can be still completed.
Yellow-purple oxide skins on the upper surface of the SUS304 stainless steel workpiece passivated by pickling with the regenerated liquid are completely removed, and white metal color appears on the surface of the passivated workpiece. And (3) passivation effect testing: NSS neutral salt spray test is carried out for 120h according to OO-P-35B requirements, the stainless steel is stainless, and the passivation performance is stable; copper sulfate titration experiment analysis shows that no copper precipitation occurs within 5 minutes.
Claims (9)
1. A preparation method of stainless steel pickling passivation solution is characterized in that,
1) preparing a raw solution:
adding concentrated sulfuric acid, sulfate and chloride into water to form an original solution;
2) preparing electrolyte by electrolyzing the raw solution:
adopting an electrode anode material: one or more of boron-doped diamond, lead oxide, glassy carbon electrode and ruthenium-titanium-iridium oxide;
adopting electrode cathode materials: one or more of boron-doped diamond, lead oxide, glassy carbon electrode, ruthenium-titanium-iridium oxide, graphite, stainless steel and lead plate;
electrolyzing the raw solution prepared in the step 1), inserting the electrode anode material and the electrode cathode material into the raw solution and connecting the electrode anode material and the electrode cathode material with a power supply, wherein under the condition of electrifying, hydroxyl radicals are generated on the surface of the anode material, sulfate ions and chloride ions of the raw solution are oxidized by the strong oxidizing property of the hydroxyl radicals to form an oxidizing agent, and the oxidizing agent comprises persulfuric acid or/and persulfate, hypochlorous acid or/and hypochlorite, perchloric acid or/and perchlorate;
3) preparing stainless steel pickling passivation solution:
adding nitric acid into the electrolyte in the step 2), adding fluoride salt or/and hydrogen fluoride salt: one or more of sodium fluoride, potassium fluoride and ammonium bifluoride; adding other additives: alcohols, thiourea and benzoic acid to finally form the stainless steel pickling passivation solution.
2. The method for preparing the stainless steel pickling passivation solution according to claim 1, wherein 2-200g of 98% concentrated sulfuric acid is added to each liter of water in the step 1); adding 0.1-250g of sodium sulfate or/and potassium sulfate; adding 0.1-300g of sodium chloride or/and potassium chloride.
3. The method for preparing the stainless steel pickling passivation solution according to claim 1, wherein the current density during electrolysis in the step 2): 5mA/cm2-1A/cm2And time: 1-120min, voltage: 2-50V.
4. The method for preparing the stainless steel pickling passivation solution according to claim 1, wherein an electrode anode material and an electrode cathode material adopted in the step 2) are boron-doped diamond.
5. The preparation method of the stainless steel pickling passivation solution as claimed in claim 1, wherein the weight components of the oxidant generated by electrolysis in step 2) are as follows: 0.01-10% of persulfate, 0.01-6% of hypochlorite and 0.01-1.1% of perchlorate.
6. The preparation method of the stainless steel pickling passivation solution according to claim 1, wherein 2-300g of nitric acid is added to each liter of electrolyte in the step 3); adding fluoride salt or/and hydrogen fluoride salt: 1-20g of one or more of sodium fluoride, potassium fluoride and ammonium bifluoride; adding other additives: 0.02-20g of glycerol, 0.01-18g of diphenylthiourea or/and thiourea and 0.1-10g of sodium benzoate or/and ammonium benzoate.
7. The stainless steel product treated by the stainless steel pickling passivation solution prepared by the method in claim 1 is characterized in that the stainless steel product to be treated is placed into the stainless steel pickling passivation solution to be soaked for 10-120min and then is washed clean by water.
8. The method for regenerating the stainless steel pickling passivation solution after the stainless steel product is treated according to claim 7, wherein after the waste solution of the stainless steel pickling passivation solution after the stainless steel product is treated is electrolyzed and the precipitate is filtered in step 2), concentrated sulfuric acid, chloride and nitric acid are added, fluoride salt or/and hydrogen fluoride salt are added, and other additives are added: alcohols, thiourea and benzoic acid to obtain the regenerated liquid of the stainless steel pickling and passivating liquid.
9. The regeneration method of the stainless steel pickling passivation solution according to claim 8, characterized in that 0-50g of 98% concentrated sulfuric acid, 0.1-10g of sodium chloride or/and potassium chloride, 2-150g of nitric acid, 0.1-3g of sodium fluoride or potassium fluoride or ammonium bifluoride, 0.02-10g of glycerol, 0.01-0.8g of dimethylthiourea or/and thiourea, and 0.1-10g of sodium benzoate or/and ammonium benzoate are added to each liter of the waste stainless steel pickling passivation solution.
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| WO2010078866A2 (en) * | 2009-01-09 | 2010-07-15 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Method and device for regenerating peroxodisulfate pickling solution |
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