CN110747481A - Method for removing oxide skin on surface of hot-rolled nickel stainless steel - Google Patents
Method for removing oxide skin on surface of hot-rolled nickel stainless steel Download PDFInfo
- Publication number
- CN110747481A CN110747481A CN201810811520.9A CN201810811520A CN110747481A CN 110747481 A CN110747481 A CN 110747481A CN 201810811520 A CN201810811520 A CN 201810811520A CN 110747481 A CN110747481 A CN 110747481A
- Authority
- CN
- China
- Prior art keywords
- acid
- sulfuric acid
- percent
- balance
- mass concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C23G1/081—Iron or steel solutions containing H2SO4
Abstract
The invention provides a method for removing oxide skin on the surface of hot-rolled nickel stainless steel, which comprises the following components in percentage by mass: 3-10% of oxidant, 0.2-4% of synergist and the balance of sulfuric acid with mass concentration of 20-30%; the oxidant is di-tert-butyl peroxide or selenic acid; the synergist is at least 2 of saponin, ferulic acid, aloe-emodin, phytic acid, nitrilotriacetic acid and polyethylene glycol 5000. The invention does not use nitric acid and hydrofluoric acid, but uses sulfuric acid water solution containing oxidant to remove the oxide skin on the surface of the stainless steel through chemical reaction. The process does not produce toxic nitrogen oxides, and is favorable for protecting the environment.
Description
Technical Field
The invention relates to a metal surface treatment technology, in particular to a method for removing oxide skin on the surface of hot-rolled nickel stainless steel, and more particularly relates to a method for removing oxide skin on the surfaces of 200 and 300 series hot-rolled nickel stainless steel plates and strips such as 201, 304, 307 and 316.
Background
The oxide skin on the surfaces of the hot-rolled nickel stainless steel plate strip and the hot-rolled nickel stainless steel plate strip mainly comprises nickel spinel, and until now, nitric acid and hydrofluoric acid are adopted by production enterprises to remove the oxide skin on the surfaces of the hot-rolled nickel stainless steel plate strip and the hot-rolled nickel stainless steel plate strip. The corresponding process flow comprises the following steps: scale breaking or shot blasting → nitric acid and inverted flock mixed solution cleaning → water washing → passivation → water washing → neutralization → water washing → drying. In the process, a large amount of toxic yellow nitrogen oxides are generated by the oxidation of nitric acid in the descaling process, and the process is commonly called as emitting yellow smoke to contaminate the atmosphere, and accompanied by the generation of intractable nitrate-state wastewater.
Under the acidic condition, hydrogen peroxide has good capability of removing oxide skin on the surface of the hot-rolled nickel stainless steel material, but the hydrogen peroxide is decomposed due to the reaction heat, and a stabilizing agent consisting of a plurality of reagents such as hydroxyethylidene diphosphonic acid, amino trimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid (sodium), butylamine phosphate-1, 2, 4 tricarboxylic acid, diethylenetriamine pentamethylene phosphonic acid, 2-hydroxyphosphonoacetic acid, water glass, ethylene diamine tetraacetic acid, polyacrylamide, diethylamine pentaacetic acid and the like needs to be added, so that the economic cost is increased, and the application of the hydrogen peroxide is restricted.
Disclosure of Invention
The invention aims to provide a method for removing oxide skin on the surface of hot-rolled nickel stainless steel, which does not use nitric acid and hydrofluoric acid and avoids the emission of nitrogen oxides; no hydrogen peroxide is used.
In order to achieve the purpose, the invention provides the following technical scheme:
an additive for removing oxide skin pickling solution on the surface of hot-rolled nickel stainless steel comprises the following components in parts by mass: 3-10 parts of oxidant and 0.2-4 parts of synergist; the oxidant is di-tert-butyl peroxide or selenic acid; the synergist is at least 2 of saponin, ferulic acid, aloe-emodin, phytic acid, nitrilotriacetic acid and polyethylene glycol 5000.
The pickling solution for removing the oxide skin on the surface of the hot-rolled nickel stainless steel comprises the following components in percentage by mass: 3-10% of oxidant, 0.2-4% of synergist and the balance of sulfuric acid with mass concentration of 20-30%; the oxidant is di-tert-butyl peroxide or selenic acid; the synergist is at least 2 of saponin, ferulic acid, aloe-emodin, phytic acid, nitrilotriacetic acid and polyethylene glycol 5000.
Further, in the present invention,
the pickling solution comprises the following components in percentage by mass: 3-10% of di-tert-butyl peroxide, 1-2% of saponin, 0.5-1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
further, in the case of a liquid crystal display,
the pickling solution comprises the following components in percentage by mass: 10 percent of di-tert-butyl peroxide, 2 percent of saponin, 0.5 percent of phytic acid and the balance of sulfuric acid with the mass concentration of 20 to 30 percent.
Alternatively, or, further,
the pickling solution comprises the following components in percentage by mass: 3-5% of di-tert-butyl peroxide, 0.2-0.5% of ferulic acid, 0.2-0.3% of aloe-emodin, 0.8-1% of nitrilotriacetic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
further, in the case of a liquid crystal display,
the pickling solution comprises the following components in percentage by mass: 3 percent of di-tert-butyl peroxide, 0.2 percent of ferulic acid, 0.3 percent of aloe-emodin, 0.8 percent of nitrilotriacetic acid and the balance of sulfuric acid with the mass concentration of 20-30 percent.
Alternatively, or, further,
the pickling solution comprises the following components in percentage by mass: 6-8% of selenic acid, 1-2% of saponin, 0.5-1% of phytic acid, 0.2-0.5% of ferulic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
further, in the case of a liquid crystal display,
the pickling solution comprises the following components in percentage by mass: selenic acid 8%, saponin 1%, phytic acid 1%, ferulic acid 0.5%, and the balance of sulfuric acid with mass concentration of 20-30%.
Alternatively, or, further,
the pickling solution comprises the following components in percentage by mass: 3-5% of selenic acid, 0.4-1% of saponin, 0.5-1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
further, in the case of a liquid crystal display,
the pickling solution comprises the following components in percentage by mass: 3% of selenic acid, 1% of saponin, 1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%.
A method for removing oxide skin on the surface of hot-rolled nickel stainless steel comprises the following steps:
scale breaking or shot blasting, acid washing, water washing, passivation, water washing, neutralization, water washing and drying;
the pickling solution adopted by pickling is the pickling solution prepared by any one of the components according to the proportion; the mass concentration of the sulfuric acid is preferably 25%; the amount of sulfuric acid at the concentration described should ensure solubility of the synergist.
The temperature of the pickling solution is 65-85 ℃, and the running speed of the strip is 18 m-25/min.
The reaction temperature of the invention is 65-85 ℃, if the temperature is increased to 100 ℃, the reaction is accelerated, and if the temperature is reduced, the reaction speed is reduced.
The invention uses oxidant di-tert-butyl peroxide and selenic acid. Inorganic chemical oxidants with the standard electrode potential of not less than +1.15V can be used for removing the oxide skin of the stainless steel materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention does not use nitric acid and hydrofluoric acid, but uses the sulfuric acid aqueous solution to remove the oxide skin on the surface of the stainless steel, and the sulfuric acid aqueous solution contains an oxidant and a synergist which can remove the oxide skin through chemical reaction under acidic conditions. The process does not produce toxic nitrogen oxides, and is favorable for protecting the environment. The present invention does not use hydrogen peroxide.
Detailed Description
Example 1
The experimental method comprises the following steps: cutting a hot-rolled nickel stainless steel sample into rectangular pieces with the width of 4cm and the length of 6cm, immersing the rectangular pieces into a sulfuric acid pickling solution at the temperature of 80-85 ℃, and observing the time required for removing an oxide skin; all sample surfaces were not shot blasted.
Preparing a pickling solution: 100mL of 25% sulfuric acid (note; mass ratio w/w: the same below), 10g of di-tert-butyl peroxide, 2g of saponin and 0.5g of phytic acid.
Sample 201 for 2 minutes, sample 304 for 8 minutes, sample 307 for 12 minutes, and sample 316 for 30 minutes.
And (3) passivating the sample after the scale is removed in 20% nitric acid for 1 minute after water washing, neutralizing the sample in a borax solution with the pH value of more than or equal to 10 and the temperature of 80 ℃ after water washing, taking out and airing the sample.
Example 2
The concrete operation is the same as that of example 1
Preparing a pickling solution: 100mL of 25% sulfuric acid, 3g of di-tert-butyl hydroperoxide, 0.2g of ferulic acid, 0.3g of aloe-emodin and 0.8g of nitrilotriacetic acid.
The time for descaling the slab band and the plate sample is 4 minutes, 15 minutes, 26 minutes and 52 minutes respectively, wherein the time for descaling the slab band and the plate sample is 304 minutes, 307 minutes and 316 minutes.
Example 3
The procedure was as in example 1.
Preparing a pickling solution: 100mL of 25% sulfuric acid, 8g of selenic acid, 1g of saponin, 1g of phytic acid and 0.5g of ferulic acid.
201. 304, 307 and 316 respectively have the following descaling time: 3, 10, 20, 48 minutes.
If 3g of selenic acid is used in the formula of the pickling solution, the descaling time of the sample is respectively; 4. 12, 25, 55 minutes.
Example 4
Removing oxide skin on the surface of a 201 plate strip with the thickness of 3mm and the width of 40 cm:
the process flow comprises the following steps: mechanical scale breaking → sulfuric acid cleaning → water washing → nitric acid normal temperature passivation → water washing → neutralization → water washing → drying
A sulfuric acid pickling tank with a length of 40m, a width of 50cm and a height of 65cm is prepared into a 25% sulfuric acid solution with a volume of 10 cubic meters (a liquid level height of 50cm) in the pickling tank.
20kg of saponin, 10kg of phytic acid and 100kg of hydrogen peroxide di-tert-butyl are added into the sulfuric acid solution.
The reaction temperature is 65 ℃, and the running speed of the plate strip is 18 m/min. Test results show that; and thoroughly removing the oxide skin.
The sulfuric acid pickling waste liquid is frozen and crystallized at the temperature of minus 5 ℃, and the sulfuric acid recovered after filtration and separation can be used for pickling again.
The method does not use nitric acid and hydrofluoric acid to remove oxide skin on the surface of the stainless steel material, does not generate toxic nitric oxide and acid pickling waste liquid which is difficult to treat, and the sulfuric acid pickling waste liquid is frozen and crystallized at the temperature of minus 5 ℃, and the sulfuric acid recovered after filtering and separation can be used for acid pickling again. Compared with the method for removing the oxide skin by using nitric acid and hydrofluoric acid, the method has the advantage of being beneficial to environmental protection; and the economic cost is lower than that of the nitric acid and hydrofluoric acid methods.
Claims (7)
1. The additive for removing the oxide skin pickling solution on the surface of the hot-rolled nickel stainless steel is characterized by comprising the following components in parts by mass: 3-10 parts of oxidant and 0.2-4 parts of synergist; the oxidant is di-tert-butyl peroxide or selenic acid; the synergist is at least 2 of saponin, ferulic acid, aloe-emodin, phytic acid, nitrilotriacetic acid and polyethylene glycol 5000.
2. The pickling solution for removing the oxide skin on the surface of the hot-rolled nickel stainless steel is characterized by comprising the following components in percentage by mass: 3-10% of oxidant, 0.2-4% of synergist and the balance of sulfuric acid with mass concentration of 20-30%; the oxidant is di-tert-butyl peroxide or selenic acid; the synergist is at least 2 of saponin, ferulic acid, aloe-emodin, phytic acid, nitrilotriacetic acid and polyethylene glycol 5000.
3. The pickling solution of claim 2 comprising the following components in weight percent: 3-10% of di-tert-butyl peroxide, 1-2% of saponin, 0.5-1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
alternatively, the first and second electrodes may be,
3-5% of di-tert-butyl peroxide, 0.2-0.5% of ferulic acid, 0.2-0.3% of aloe-emodin, 0.8-1% of nitrilotriacetic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
alternatively, the first and second electrodes may be,
6-8% of selenic acid, 1-2% of saponin, 0.5-1% of phytic acid, 0.2-0.5% of ferulic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
alternatively, the first and second electrodes may be,
3-5% of selenic acid, 0.4-1% of saponin, 0.5-1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%.
4. The pickling solution of claim 3 comprising the following components in weight percent: 10 percent of di-tert-butyl peroxide, 2 percent of saponin, 0.5 percent of phytic acid and the balance of sulfuric acid with the mass concentration of 20 to 30 percent;
alternatively, the first and second electrodes may be,
3 percent of di-tert-butyl peroxide, 0.2 percent of ferulic acid, 0.3 percent of aloe-emodin, 0.8 percent of nitrilotriacetic acid and the balance of sulfuric acid with the mass concentration of 20-30 percent;
alternatively, the first and second electrodes may be,
8% of selenic acid, 1% of saponin, 1% of phytic acid, 0.5% of ferulic acid and the balance of sulfuric acid with the mass concentration of 20-30%;
alternatively, the first and second electrodes may be,
3% of selenic acid, 1% of saponin, 1% of phytic acid and the balance of sulfuric acid with the mass concentration of 20-30%.
5. The acid wash of claim 2, 3 or 4 wherein the sulfuric acid has a mass concentration of 25%.
6. A method for removing oxide skin on the surface of hot-rolled nickel stainless steel comprises the following steps: scale breaking or shot blasting, acid washing, water washing, passivation, water washing, neutralization, water washing and drying; the method is characterized in that:
the pickling solution used for the pickling is the pickling solution according to any one of claims 2 to 4;
the temperature of the pickling solution is 65-85 ℃, and the running speed of the strip is 18 m-25/min.
7. The method for descaling the surface of hot-rolled nickel stainless steel according to claim 6, wherein the sulfuric acid concentration in the pickling solution is 25% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810811520.9A CN110747481A (en) | 2018-07-23 | 2018-07-23 | Method for removing oxide skin on surface of hot-rolled nickel stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810811520.9A CN110747481A (en) | 2018-07-23 | 2018-07-23 | Method for removing oxide skin on surface of hot-rolled nickel stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110747481A true CN110747481A (en) | 2020-02-04 |
Family
ID=69274896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810811520.9A Pending CN110747481A (en) | 2018-07-23 | 2018-07-23 | Method for removing oxide skin on surface of hot-rolled nickel stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110747481A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950014377A (en) * | 1993-11-23 | 1995-06-16 | 조말수 | Descaling method of martensitic stainless steel |
| CN103343345A (en) * | 2013-07-24 | 2013-10-09 | 太仓市协诚金属制品有限公司 | Novel environment-friendly polishing process for stainless steel metal product |
| CN105499287A (en) * | 2015-12-29 | 2016-04-20 | 何百寅 | Method for removing scales of hot-rolled nickel and chromium stainless steel materials |
| CN105908197A (en) * | 2016-06-22 | 2016-08-31 | 山西艾尔德添加剂新技术有限公司 | Pickling additive for surface oxide scale of stainless steel material and preparation method therefor and pickling method thereof |
| CN107460491A (en) * | 2017-08-10 | 2017-12-12 | 武汉众登科技有限公司 | A kind of environment-friendly hot rolling low chrome ferritic stainless steel acid washing method |
-
2018
- 2018-07-23 CN CN201810811520.9A patent/CN110747481A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950014377A (en) * | 1993-11-23 | 1995-06-16 | 조말수 | Descaling method of martensitic stainless steel |
| CN103343345A (en) * | 2013-07-24 | 2013-10-09 | 太仓市协诚金属制品有限公司 | Novel environment-friendly polishing process for stainless steel metal product |
| CN105499287A (en) * | 2015-12-29 | 2016-04-20 | 何百寅 | Method for removing scales of hot-rolled nickel and chromium stainless steel materials |
| CN105908197A (en) * | 2016-06-22 | 2016-08-31 | 山西艾尔德添加剂新技术有限公司 | Pickling additive for surface oxide scale of stainless steel material and preparation method therefor and pickling method thereof |
| CN107460491A (en) * | 2017-08-10 | 2017-12-12 | 武汉众登科技有限公司 | A kind of environment-friendly hot rolling low chrome ferritic stainless steel acid washing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4238244A (en) | Method of removing deposits from surfaces with a gas agitated cleaning liquid | |
| HRP20181045T1 (en) | Process for pickling silicon-containing electrical steel with an acidic pickling solution containing ferric ions | |
| CN103882455A (en) | Nitric-acid-free stainless steel acid washing solution and preparation method thereof | |
| US3756957A (en) | Solutions for chemical dissolution treatment of metallic materials | |
| CN114592196A (en) | Environment-friendly neutral rust remover and preparation method thereof | |
| CN102020280B (en) | Method for inhibiting yellow smog during pickling of silicon materials | |
| CN109457259A (en) | A kind of stainless steel derusting and cleaning agent | |
| US3856694A (en) | Process for stripping nickel from articles and composition utilized therein | |
| CN1195102C (en) | Acid pickling promotor for iron and steel | |
| US5496449A (en) | Method of treating salt bath liquid | |
| CN110747481A (en) | Method for removing oxide skin on surface of hot-rolled nickel stainless steel | |
| CN101285196A (en) | Processing technology for surface oxide skin of aviation tubes | |
| CN108359999A (en) | A kind of brass wire environmental protection pickle and its methods for making and using same | |
| US5417775A (en) | Process for continuous titanium sheet pickling and passivation without using nitric acid | |
| KR101582554B1 (en) | Manufacturing method of pure nickel plate from high fluorine containing nickel slime and treatment of acid washing and water washing solution of nickel slime | |
| US3583867A (en) | Compositions for and method of dissolving nickel | |
| KR101482314B1 (en) | The method and apparatus for efficient pickling of hot rolled steel | |
| CN114622213A (en) | Environment-friendly neutral copper pickling solution | |
| CN114000155A (en) | Universal aluminum and aluminum alloy environment-friendly dedusting agent | |
| KR101437357B1 (en) | Composition for removal of the oxide layer and the scale and the preparation method thereof | |
| US3529998A (en) | Pickling process | |
| Narvaez et al. | Hydrogen peroxide decomposition in an environmentally friendly pickling solution for AISI 316L stainless steel | |
| CN104805447B (en) | Preparation method of acid fogging inhibitor | |
| JPS602392B2 (en) | Pickling method for stainless steel that suppresses NOx generation | |
| US3647686A (en) | Method of treating industrial waste water without contamination of the environment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |