CN102719839A - Pickling agent for stainless steel - Google Patents
Pickling agent for stainless steel Download PDFInfo
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- CN102719839A CN102719839A CN2012102136045A CN201210213604A CN102719839A CN 102719839 A CN102719839 A CN 102719839A CN 2012102136045 A CN2012102136045 A CN 2012102136045A CN 201210213604 A CN201210213604 A CN 201210213604A CN 102719839 A CN102719839 A CN 102719839A
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Abstract
The invention relates to a pickling agent for stainless steel. According to percentage by weight, the pickling agent consists of the following components: 23 to 30 percent of sulfuric acid; 4 to 6 percent of nitric acid; 7 to 14 percent of hydrochloric acid; 0.1 to 0.3 percent of corrosion inhibitor; 0.13 to 0.25 percent of additive; and the balance of water. The mass concentrations of the used acids are as follows: 95.0 to 98.0 percent of sulfuric acid; 65.0 to 68.0 percent of nitric acid; and 36.0 to 38.0 percent of hydrochloric acid. The components are uniformly mixed according to proportion. The corrosion inhibitor is hexamethylene tetramine, the additive is the mixture of sodium dodecyl sulfate and isooctyl phenol polyoxyethylene, the percentage by weight of the sodium dodecyl sulfate is 0.08 to 0.15 percent, the percentage by weight of the isooctyl phenol polyoxyethylene is 0.05 to 0.1 percent, and the effect is better when the temperature of each acid is 60 DEG C to 80 DEG C. The pickling efficiency of the pickling agent for stainless steel is increased by four to five times, the pickled surface is bright and clean, and the pickling agent for stainless steel is particularly suitable for pickling the surfaces of stainless steel with high Cr, Ni and Mo alloy contents to remove ferric oxide scales.
Description
Technical field
The present invention relates to a kind of stainless pickling agent, refer to a kind of Cr, Ni, the higher stainless steel surface scale oxide removal chemical pickling agent of Mo alloy content especially.
Background technology
Corrosion resisting stainless steels such as super austenitic 904L and 2205 duplex stainless steels; Chromium, nickel, molybdenum alloy constituent content are respectively 19.00～23.00,4.00～26.00 and 3.00～5.00 percent; Have also to contain 1.00～2.00 percent copper and carbon content lower; Have very good anti-corrosion, the corrosion-resistant characteristic outstanding behaviours is in the following aspects: (1) performance of good anti-general corrosion under phosphoric acid and sulphuric acid environment; (2) the good anti-pitting attack and the performance of crevice corrosion; (3) compare with content percent 18-8 or 18-8-Mo class stainless steel, have the performance of more outstanding stress corrosion dehiscence resistant; (4) good anti intercrystalline corrosion performance.Thereby be widely used in some harsh industrial environments such as sulfuric acid production, chemical plant installations, heat exchanger, pharmacy, papermaking, WWT.
Yet before 2003, because China's stainless steel industry development is slower, technical equipment falls behind, so the corrosion resisting stainless steel of China's demand all relies on import.Along with the raising of China's Stainless Steel Production equipment technology and the capacity of scientific research, more domestic large-size stainless steel enterprises can carry out small serial production in recent years.Know that as people stainless Industrial processes comprise smelting, refining, casting, preheating, hot rolling at high temperature and annealing, pickling, cold rolling and precision work at room temperature.Pickling is to adopt the method for machinery, electrochemistry or chemistry to remove the scale oxide that stainless steel surface forms in the high temperature process process.Corrosion resisting stainless steel Cr content is high, contain higher Ni and a certain amount of Mo simultaneously.Scale oxide layer complex structure contains iron protoxide (FeO), red stone (Fe
2O
3), Z 250 (Fe
3O
4), chromic oxide (Cr
2O
3), nickel oxide (NiO), silicon-dioxide (SiO
2), picotite (Cr
2O
3FeO) and nickel spinel (NiFe
2O
3) etc., possibly also have the oxide compound of Mo, the result makes the scale oxide compact structure, and with the strong adhesion of matrix, adopt existing traditional hot vitriol oil soak acid-cleaning technology to carry out pickling, on the one hand the pickling time long, production efficiency is low; The long-time oxide debris of soaking in some zone is still removed not exclusively on the other hand, and causes stainless steel surface coarse and matt, has had a strong impact on the stainless steel surface quality.Pickling has become one of bottleneck of restriction corrosion resisting stainless steel batch process.
Summary of the invention
The present invention is long in order to solve the existing stainless steel oxidation iron scale pickling time, and pickling efficient is low, and the problem of surface quality difference after the pickling provides the residual stainless pickling agent of stainless steel surface non-oxidation iron scale after a kind of pickling efficient height, the pickling.
Stainless steel needs in Industrial processes through hot procedures such as heating, hot rolling, annealing; Through a series of like this high-temperature technology process surface of steel plate oxidizing reaction can take place form the fine and close scale oxide layer of black; Scale oxide not only influences stainless visual appearance; Also can the following process of steel plate be had a negative impact, so before following process, must adopt surface treatment methods such as pickling, polishing to be removed.The stainless steel oxidation iron scale is Cr
2O
3, FeO.Cr
2O
3, NiO, FeO.Cr
2O.Fe
2O
3Deng dense oxide, it is different because of the difference of the stainless steel trade mark, process for processing condition to remove difficulty.Corrosion resisting stainless steel contains a certain amount of Mo simultaneously owing to contain higher Cr, Ni, makes that the composition structure of scale oxide is more complicated, fine and close, also more is difficult to remove.
Corrosion resisting stainless steel is in Industrial processes; When adopting the pickling of the traditional hot vitriol oil; Oxide compound in the surface oxidation iron scale is difficult to dissolving in sulfuric acid; Need to soak 3 ~ 5h, acid solution can be got off scale oxide by the swelling pressure that this part hydrogen produces slowly through weak part and the iron in micro gap and the scale oxide, chromium or a large amount of hydrogen of iron matrix effect generation of scale oxide from the stainless steel sur-face peeling.In this way during pickling, the one, because the corrosion resisting stainless steel scale oxide is fine and close, tough and tensile, the speed that acid solution is infiltrated is very slow, and soak time is long, and production efficiency is low; The 2nd, because the scale oxide structure is inhomogeneous, some regional scale oxide is very fine and close, and acid solution is difficult to infiltrate; Other regional scale oxides have been removed and have been exposed matrix, and the removal of scale oxide is very inhomogeneous.The long-time immersion makes the part that exposes matrix that corrosion take place, and causes mattness.
In order to remove the scale oxide on corrosion resisting stainless steel surface quickly and efficiently, solve corrosion resisting stainless steel industrial mass manufacture bottleneck problem.The present invention discloses a kind of effective pickling agent.
The present invention is in traditional hot concentrated sulfuric acid pickling agent; Add hydrochloric acid, nitric acid and an amount of additive; Because hydrochloric acid belongs to strong reducing property acid, very high degree of ionization is arranged, effectively the red stone in the dissolved oxygen iron scale; For sulfuric acid passes through the scale oxide layer passage is provided, has promoted the effect of vitriolic mechanically peel.Nitric acid has stronger oxidisability, can make the difficult Cr that reacts with pickle solution in the stainless steel surface scale oxide
2O
3Structure changes, and has accelerated the speed that sulfuric acid infiltrates the scale oxide bottom, strengthens pickling effect.In order to slow down the stainless steel base corrosion, prevent to inhale hydrogen and acid mist volatilization diffusion simultaneously, added an amount of additive.
This stainless pickling agent, composed of the following components by mass percentage:
Sulfuric acid 23～30%; Nitric acid 4～6%; Hydrochloric acid 7～14%;
Inhibiter 0.1～0.3 %; Additive 0.13～0.25%;
All the other are water.
The mass concentration of used acid is respectively:
Sulfuric acid 95.0%～98.0%; Nitric acid 65.0%～68.0%; Hydrochloric acid 36.0～38.0%
Above-mentioned each component is proportionally stirred.
Above-mentioned stainless pickling agent is characterized in that: described inhibiter is a hexamethylenetetramine.
Above-mentioned stainless pickling agent is characterized in that: described additive is the miscellany of sodium lauryl sulphate and second octyl phenol polyoxy ethene (10 ether) (also claiming OP-10), and both mass percents are:
Sodium lauryl sulphate 0.08～0.15%; Second octyl phenol polyoxy ethene (10 ether) 0.05～0.1%.
Above-mentioned stainless pickling agent is characterized in that: each sour temperature is 60～80 ℃.
Heating temperature reduces along with treating pickling steel grade interalloy elemental nickel content to improve.Corrosion resisting stainless steel is immersed wherein, soak 8～15min, pull out with flushing with clean water and totally get final product.
The present invention compares with traditional sulphuric acid soln with the mixing solutions that reasonable, accurate mixed obtains sulfuric acid, nitric acid, hydrochloric acid and additive; The former and scale oxide react; Cleansing power is strong; Lighter to the metallic matrix corrosion, inhibiter can obtain good surface quality to the effective provide protection of steel in addition.Adopt this pickling agent for stainless steel to replace used sulfuric acid, can significantly shorten the pickling time, pickling efficient has improved 4～5 times, and any surface finish after the pickling is fair and clear, and the non-oxidation iron scale is residual, has solved one of industrial bottleneck problem of batch of corrosion resisting stainless steel.Excellent its is applicable to as Cr, Ni, the higher stainless steel surface scale oxide of Mo alloy content removes the chemical pickling agent.
Embodiment
Specify embodiment of the present invention below in conjunction with embodiment, but embodiment of the present invention is not limited to following embodiment.
EmbodimentThe application of 1 this pickle solution in the big production pickling of 904L plate.
In the pickling tank of long 9.1m, wide 2.65m, dark 3.2m, according to mass percent:
Sulfuric acid 28%; Nitric acid 5%; Hydrochloric acid 10%; Hexamethylenetetramine 0.15%;
Sodium lauryl sulphate 0.1%; Second octyl phenol polyoxy ethene (10 ether) 0.08%; All the other are water.
The mass concentration of used acid is respectively:
Sulfuric acid 96.0%; Nitric acid 66.0%; Hydrochloric acid 37.0%
Prepared 62m
3Pickle solution.Pickle solution slowly is heated to 65 ℃, will fills plate among the 904L behind the thermal treatment shot-peening (thickness 10mm) pickling basket then and hang in the pickling tank behind the 8min, hang out behind the pickling basket surface of steel plate is clean with high pressure water washing.Product surface oxide debris be removed and any surface finish fair and clear.
EmbodimentThe application of 2 these pickle solutions in the big production pickling of 2205 duplex stainless steels
In the pickling tank of long 9.1m, wide 2.65m, dark 3.2m, according to mass percent:
Sulfuric acid 30%; Nitric acid 5%; Hydrochloric acid 12%; Hexamethylenetetramine 0.2 %;
Sodium lauryl sulphate 0.1%; Second octyl phenol polyoxy ethene (10 ether) 0.1%; All the other are water.
The mass concentration of used acid is respectively:
Sulfuric acid 96.0%; Nitric acid 66.0%; Hydrochloric acid 37.0%
Prepared 60m
3Pickle solution.Pickle solution slowly is heated to 80 ℃, will fills plate in 2205 duplex stainless steels behind the thermal treatment shot-peening (thickness 8mm) pickling basket then and hang in the pickling tank behind the 12min, hang out behind the pickling basket surface of steel plate is clean with high pressure water washing.Product surface oxide debris be removed and any surface finish fair and clear.
Claims (6)
1. stainless pickling agent, composed of the following components by mass percentage:
Sulfuric acid 23～30%; Nitric acid 4～6%; Hydrochloric acid 7～14%;
Inhibiter 0.1～0.3 %; Additive 0.13～0.25%;
All the other are water;
The mass concentration of used acid is respectively:
Sulfuric acid 95.0%～98.0%; Nitric acid 65.0%～68.0%; Hydrochloric acid 36.0～38.0%
Above-mentioned each component is proportionally stirred.
2. stainless pickling agent according to claim 1 is characterized in that: described inhibiter is a hexamethylenetetramine.
3. according to claim 1 or 2 said stainless pickling agents, it is characterized in that: described additive is the miscellany of sodium lauryl sulphate and second octyl phenol polyoxy ethene, and both mass percents are:
Sodium lauryl sulphate 0.08～0.15%; Second octyl phenol polyoxy ethene 0.05～0.1%.
4. according to the said stainless pickling agent of claim 3, it is characterized in that: each sour temperature is 60～80 ℃.
5. stainless pickling agent according to claim 1 and 2 is characterized in that: each sour temperature is 60～80 ℃.
6. stainless pickling agent according to claim 4 is characterized in that the pickling time is 8～15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102136045A CN102719839A (en) | 2012-06-27 | 2012-06-27 | Pickling agent for stainless steel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102136045A CN102719839A (en) | 2012-06-27 | 2012-06-27 | Pickling agent for stainless steel |
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| CN102719839A true CN102719839A (en) | 2012-10-10 |
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|---|---|---|---|
| CN2012102136045A Pending CN102719839A (en) | 2012-06-27 | 2012-06-27 | Pickling agent for stainless steel |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498185A (en) * | 2013-09-03 | 2014-01-08 | 湖北实美科技有限公司 | Low-temperature polishing solution |
| CN105274541A (en) * | 2014-07-17 | 2016-01-27 | 烟台盛业钢格板有限公司 | Composite for surface treatment of stainless steel grating plate |
| CN108220976A (en) * | 2017-12-29 | 2018-06-29 | 中国大唐集团科学技术研究院有限公司火力发电技术研究所 | Cr steel oxidation object cleaning agents material compositions, cleaning agent, preparation method and application |
| CN108517527A (en) * | 2018-05-04 | 2018-09-11 | 浙江恒利五金科技有限公司 | inorganic acid rust remover and preparation method thereof |
| CN111850573A (en) * | 2020-07-15 | 2020-10-30 | 北京首钢吉泰安新材料有限公司 | Steel pickling pretreatment method and product thereof |
| CN113481498A (en) * | 2021-06-30 | 2021-10-08 | 东风商用车有限公司 | Surface straw acidification lubrication treatment method for heat-resistant steel wire |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002722A (en) * | 2009-08-28 | 2011-04-06 | 比亚迪股份有限公司 | Stainless steel cleaner and stainless steel cleaning method |
-
2012
- 2012-06-27 CN CN2012102136045A patent/CN102719839A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002722A (en) * | 2009-08-28 | 2011-04-06 | 比亚迪股份有限公司 | Stainless steel cleaner and stainless steel cleaning method |
Non-Patent Citations (2)
| Title |
|---|
| 余存烨: "关于不锈钢设备与零部件酸洗配方讨论", 《清洗世界》, vol. 22, no. 11, 31 December 2006 (2006-12-31) * |
| 郭丽娟 等: "不锈钢氧化皮的酸洗", 《五金科技》, vol. 28, no. 1, 28 February 2000 (2000-02-28) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498185A (en) * | 2013-09-03 | 2014-01-08 | 湖北实美科技有限公司 | Low-temperature polishing solution |
| CN103498185B (en) * | 2013-09-03 | 2016-08-17 | 湖北实美科技有限公司 | Cryogenic polishing liquid |
| CN105274541A (en) * | 2014-07-17 | 2016-01-27 | 烟台盛业钢格板有限公司 | Composite for surface treatment of stainless steel grating plate |
| CN108220976A (en) * | 2017-12-29 | 2018-06-29 | 中国大唐集团科学技术研究院有限公司火力发电技术研究所 | Cr steel oxidation object cleaning agents material compositions, cleaning agent, preparation method and application |
| CN108517527A (en) * | 2018-05-04 | 2018-09-11 | 浙江恒利五金科技有限公司 | inorganic acid rust remover and preparation method thereof |
| CN111850573A (en) * | 2020-07-15 | 2020-10-30 | 北京首钢吉泰安新材料有限公司 | Steel pickling pretreatment method and product thereof |
| CN113481498A (en) * | 2021-06-30 | 2021-10-08 | 东风商用车有限公司 | Surface straw acidification lubrication treatment method for heat-resistant steel wire |
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Application publication date: 20121010 |