CN101333665A - Pickle liquor for removing mill furnace cinder of hot-rolled chromium stainless steel and method for removing mill furnace cinder - Google Patents
Pickle liquor for removing mill furnace cinder of hot-rolled chromium stainless steel and method for removing mill furnace cinder Download PDFInfo
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- CN101333665A CN101333665A CNA2008100550453A CN200810055045A CN101333665A CN 101333665 A CN101333665 A CN 101333665A CN A2008100550453 A CNA2008100550453 A CN A2008100550453A CN 200810055045 A CN200810055045 A CN 200810055045A CN 101333665 A CN101333665 A CN 101333665A
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Abstract
The invention provides an acid lotion for removing an oxide coating of hot-rolled chromium stainless steel and a method for removing the oxide coating, wherein the acid lotion is prepared by mixing sulfuric acid which is adopted as a pickling medium and Aliphatic Amine hydrochloride, Trichloroisocyanuric Acid, mannich hydrochloride and thiourea which are adopted as additives. The method for removing the oxide coating comprises the following steps: firstly, the hot-rolled chromium stainless steel wire rod is immersed into the acid lotion; secondly, the acid lotion is warmed up to 80-90 DEG C to react for 100 to 120 minutes; and thirdly, the wire rod is taken out and rinsed with high-pressure water to remove the oxide coating. The acid lotion can effectively remove the oxide coating of the hot-rolled chromium stainless steel, and particularly has good effect of removing oxide coatings for 1Cr13, 2Cr13 and 3Cr13 wire rods. The acid lotion can also be used for removing an oxide coating of hot-rolled nickel stainless steel. The acid lotion uses neither nitric acid nor hydrofluoric acid and has the advantage of environmental protection.
Description
Technical field
The present invention relates to remove hot-rolled stainless steel oxide skin technology, particularly remove the technology of hot-rolled chromium stainless steel oxide skin, specifically is a kind of method of removing the pickle solution and the scale removal of hot-rolled chromium stainless steel oxide skin.
Background technology
The oxide skin that is generated during the stainless steel high temperature hot rolling has the spinel structure feature, picotite Cr
2O
3FeO not with sulfuric acid reaction, and can with fused ammonium persulphate generation redox reaction.So the structure of the disruptive oxidation skin of available redox reaction, loose scale removal.According to these principles of chemistry, the technology of the scale removal that the countries in the world enterprises of producing stainless steel is adopted is: high-temperature molten salt alkali soaks then and carries out pickling to reach the purpose of scale removal with nitric acid, hydrofluoric acid mixing acid.
High-temperature molten salt alkali soaks and is divided into two types of oxidized form salt bath and reduced form salt baths:
The oxidized form salt bath mixes by a certain percentage with SODIUMNITRATE, sodium hydroxide, sodium-chlor, forms congruent melting liquid down at 480-550 ℃, and stainless material is immersed in this salt bath, makes picotite carry out oxidizing reaction, so that loose scale.Its principal reaction is:
Sodium hydroxide becomes chromium trioxide and is soluble in sour chromite, promptly
Cr
2O
3+2NaOH＝2NaCrO
2+H
2O
SODIUMNITRATE makes chromite be oxidized to water-soluble chromic salt rapidly:
2NaCrO
2+3NaNO
3+2NaOH＝2Na
2CrO
4+3NaNO
2+H
2O
Reduced form salt bath composition is 20%NaH+72%NaOH+8%Na
2O about 400 ℃, reduces the fusion effect with NaH to oxide skin, makes the oxide compound of metals such as Fe in the oxide skin, Ni, Cr be reduced to metal or suboxide, and its chemical equation is:
FeO+NaH＝Fe+NaOH
Fe
3O
4+4NaH＝3Fe+4NaOH
Cr
2O
3+NaH＝2CrO+NaOH
NiO+NaH＝Ni+NaOH
Easy-to-use diluted acids such as reduzate CrO and Fe, Ni and washing are gone.
Recent decades, enterprises of producing stainless steel was continued to use this method removal hot-rolled stainless steel oxide skin, but this technical matters has high energy consumption, high chemical material consumption, oxynitride, the high shortcoming of fluorochemical processing costs.Therefore, removing high temperature alkali soaks the existing further investigation of scale removal technology of step and multinomial patent disclosure is arranged.For example:
Chinese patent 20071006665.3 discloses direct chromium stainless-steel pickling agent, and working concentration is 30% hydrochloric acid 30%-80%, and the mixing solutions of the hydrofluoric acid 17.2%-69.7% of concentration 50% is as pickling agent.U.S. Properties Inc. AK adopts HF/H at Chinese patents 02808828.X
2SO
4/ H
2O
2Chinese patent 93111022.X adopts nitric acid/hydrofluoric acid/hydrogen peroxide.Chinese patent 200510020976.6 adopts nitric acid 1-50%, hydrochloric acid 5-50%, ammonium persulphate 0.5-8%.
Use nitric acid, hydrofluoric acid need handle oxynitride in the gas phase and nitrate and the fluorochemical in hydrogen fluoride and the liquid phase in the above-mentioned technology, not only bring the pressure of environment protection, also increased running cost.
Summary of the invention
The object of the present invention is to provide a kind of pickle solution of the removal hot-rolled chromium stainless steel oxide skin that neither needs high-temperature molten salt alkali to soak also not use nitric acid, hydrofluoric acid, and the method for removing hot-rolled chromium stainless steel oxide skin with this pickle solution.
A kind of pickle solution of removing hot-rolled chromium stainless steel oxide skin provided by the invention, components based on weight percentage comprises:
Concentration is 98% sulfuric acid 10-40
TCCA (Trichloroisocyanuric acid) 1-4
The hydrochloride 2-7 of aliphatic amide
Mannich alkali salt hydrochlorate 0.1-0.5
Thiocarbamide 0.5-1.2
Water surplus.
The hydrochloride of described aliphatic amide is methylamine hydrochloride, ethylamine hydrochloride or ethylenediamine-hydrochloride etc.
Described mannich alkali salt hydrochlorate is CH
3COCH
2CH
2N (CH
3)
2HCl or CH
3CH
2COCH
2CH
2N (CH
3)
2HCl etc.
Can in pickle solution, add an amount of tensio-active agent such as peregal, Sodium palmityl sulfate etc.
The pickle solution compound method: sulfuric acid is joined in an amount of water, add other component then in proportion, add water again to required amount, stirring gets final product.
A kind of method of removing hot-rolled chromium stainless steel oxide skin immerses the hot-rolled chromium stainless steel wire rod in the above-mentioned pickle solution, is warming up to 80-90 ℃ of reaction 100-120 minute then, takes out wire rod, uses the high pressure water washing scale removal.
Perhaps: above-mentioned pickle solution at room temperature immerses the hot-rolled chromium stainless steel wire rod wherein, soaks 24-30 hour, takes out wire rod, water flushing scale removal, and oxide skin can all come off.
Described hot-rolled chromium stainless steel wire rod is 1Cr13,2Cr13,3Cr13 wire rod etc.
Compared with prior art, pickle solution of the present invention is pickling medium with sulfuric acid, can effectively remove hot-rolled chromium stainless steel oxide skin under the effect of additive, and particularly to 1Cr13,2Cr13,3Cr13 wire rod, the scale removal effect is good.Pickle solution of the present invention also can be used for removing hot rolling nickel stainless steel oxide skin.The present invention does not use nitric acid, hydrofluoric acid, has environment-friendly advantage.
Embodiment
Embodiment 1: pickle solution component and proportioning
Concentration is 98% sulfuric acid 10Kg
Ethylenediamine-hydrochloride 5Kg
TCCA (Trichloroisocyanuric acid) 1Kg
CH
3COCH
2CH
2N(CH
3)
2HCl 0.1Kg
Thiocarbamide 0.5Kg
Water 83.4Kg
In above-mentioned 100Kg pickle solution, add 30Kg 1Cr13 wire rod, reaction is 100 minutes when being warming up to 90 ℃, takes out wire rod, and the water scale sluicing is all removed, and wire rod is silvery white frosting, no excessive erosion phenomenon.
Embodiment 2: pickle solution component and proportioning
Concentration is 98% sulfuric acid 40Kg
Ethylenediamine-hydrochloride 4Kg
TCCA (Trichloroisocyanuric acid) 2Kg
CH
3CH
2COCH
2CH
2N(CH
3)
2HCl 0.5Kg
Thiocarbamide 1Kg
Water 52.5Kg
In above-mentioned 100Kg pickle solution, add 30Kg 3Cr13 wire rod, reaction is 120 minutes when being warming up to 90 ℃, takes out wire rod, and the water scale sluicing is all removed, and wire rod is silvery white frosting, no excessive erosion phenomenon.
Embodiment 3: pickle solution component and proportioning
Concentration is 98% sulfuric acid 20Kg
Methylamine hydrochloride 3Kg
TCCA (Trichloroisocyanuric acid) 4Kg
CH
3COCH
2CH
2N(CH
3)
2HCl 0.3Kg
Thiocarbamide 0.8Kg
Water 71.9Kg
In above-mentioned 100Kg pickle solution, add 30Kg 2Cr13 wire rod, reaction is 120 minutes when being warming up to 80 ℃, takes out wire rod, and the water scale sluicing is all removed, and wire rod is silvery white frosting, no excessive erosion phenomenon.
Embodiment 4: pickle solution component and proportioning
Concentration is 98% sulfuric acid 25Kg
Ethylenediamine-hydrochloride 2Kg
TCCA (Trichloroisocyanuric acid) 3Kg
CH
3CH
2COCH
2CH
2N(CH
3)
2HCl 0.3Kg
Thiocarbamide 1.2Kg
Water 68.5Kg
In above-mentioned 100Kg pickle solution, add 30Kg 1Cr13 wire rod, at room temperature soak 24 hours, but scale removal.
Embodiment 5: pickle solution component and proportioning
Concentration is 98% sulfuric acid 15Kg
Ethylenediamine-hydrochloride 3.5Kg
TCCA (Trichloroisocyanuric acid) 3Kg
CH
3COCH
2CH
2N(CH
3)
2HCl 0.25Kg
Thiocarbamide 0.7Kg
Water 77.55Kg
Embodiment 6: pickle solution component and proportioning
Concentration is 98% sulfuric acid 30Kg
Ethylenediamine-hydrochloride 2.5Kg
TCCA (Trichloroisocyanuric acid) 2.5Kg
CH
3CH
2COCH
2CH
2N(CH
3)
2HCl 0.3Kg
Thiocarbamide 0.6Kg
Water 64.1Kg
Embodiment 7: pickle solution component and proportioning
Concentration is 98% sulfuric acid 15Kg
Ethylamine hydrochloride 7Kg
TCCA (Trichloroisocyanuric acid) 1.5Kg
CH
3COCH
2CH
2N(CH
3)
2HCl 0.35Kg
Thiocarbamide 0.6Kg
Peregal 0.02Kg
Water 75.53Kg.
Claims (4)
1, a kind of pickle solution of removing hot-rolled chromium stainless steel oxide skin is characterized in that components based on weight percentage comprises:
Concentration is 98% sulfuric acid 10-40
TCCA (Trichloroisocyanuric acid) 1-4
The hydrochloride 2-7 of aliphatic amide
Mannich alkali salt hydrochlorate 0.1-0.5
Thiocarbamide 0.5-1.2
Water surplus.
2, the pickle solution of removal hot-rolled chromium stainless steel oxide skin as claimed in claim 1 is characterized in that, the hydrochloride of described aliphatic amide is methylamine hydrochloride, ethylamine hydrochloride or ethylenediamine-hydrochloride.
3, the pickle solution of removal hot-rolled chromium stainless steel oxide skin as claimed in claim 1 is characterized in that, described mannich alkali salt hydrochlorate is CH
3COCH
2CH
2N (CH
3)
2HCl or CH
3CH
2COCH
2CH
2N (CH
3)
2HCl.
4, a kind of method of removing hot-rolled chromium stainless steel oxide skin is characterized in that, the hot-rolled chromium stainless steel wire rod is immersed in the described pickle solution of claim 1, is warming up to 80-90 ℃ of reaction 100-120 minute then, takes out wire rod, uses the high pressure water washing scale removal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810055045A CN100577880C (en) | 2008-06-04 | 2008-06-04 | Pickle liquor for removing mill furnace cinder of hot-rolled chromium stainless steel and method for removing mill furnace cinder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810055045A CN100577880C (en) | 2008-06-04 | 2008-06-04 | Pickle liquor for removing mill furnace cinder of hot-rolled chromium stainless steel and method for removing mill furnace cinder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101333665A true CN101333665A (en) | 2008-12-31 |
| CN100577880C CN100577880C (en) | 2010-01-06 |
Family
ID=40196544
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810055045A Expired - Fee Related CN100577880C (en) | 2008-06-04 | 2008-06-04 | Pickle liquor for removing mill furnace cinder of hot-rolled chromium stainless steel and method for removing mill furnace cinder |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN105274544A (en) * | 2015-10-28 | 2016-01-27 | 金堆城钼业股份有限公司 | Method for quickly processing surface oxidation layer of rolled-state molybdenum product |
| CN105543865A (en) * | 2015-12-25 | 2016-05-04 | 安徽工业大学 | 400-series stainless steel annealing wire catalytic pickling solution and pickling method |
-
2008
- 2008-06-04 CN CN200810055045A patent/CN100577880C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN105274544A (en) * | 2015-10-28 | 2016-01-27 | 金堆城钼业股份有限公司 | Method for quickly processing surface oxidation layer of rolled-state molybdenum product |
| CN105543865A (en) * | 2015-12-25 | 2016-05-04 | 安徽工业大学 | 400-series stainless steel annealing wire catalytic pickling solution and pickling method |
| CN105543865B (en) * | 2015-12-25 | 2018-08-03 | 安徽工业大学 | 400 series stainless steels of one kind annealing wire rod catalysis pickle and acid washing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100577880C (en) | 2010-01-06 |
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