CN102212758A - High-alloy stainless steel for impurity-containing dilute sulphuric acid medium and processing method thereof - Google Patents
High-alloy stainless steel for impurity-containing dilute sulphuric acid medium and processing method thereof Download PDFInfo
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- CN102212758A CN102212758A CN 201110134627 CN201110134627A CN102212758A CN 102212758 A CN102212758 A CN 102212758A CN 201110134627 CN201110134627 CN 201110134627 CN 201110134627 A CN201110134627 A CN 201110134627A CN 102212758 A CN102212758 A CN 102212758A
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Abstract
The invention relates to stainless steel and a processing method thereof. In the technical scheme provided by the invention, high-alloy stainless steel for an impurity-containing dilute sulphuric acid medium is characterized by comprising the following components in percentage by weight: 19-21% of chromium, 18-26% of nickel, 6-7% of molybdenum, 0.5-1.5% of copper, 0.15-0.3% of nitrogen, 0.005-0.04% of rare earth and the balance of iron. In the technical scheme, a method for processing the high-alloy stainless steel for the impurity-containing dilute sulphuric acid medium is characterized in that the hot processing of the stainless steel is carried out in a manner of forging or rolling; the forging deformation temperature is 1150-1200 degrees centigrade; the final forging temperature is 950-1050 degrees centigrade; the beginning rolling temperature is 1100-1200 degrees centigrade; and the final rolling temperature is 900-1000 degrees centigrade. The high-alloy stainless steel in the scheme can satisfy use requirements of the impurity-containing dilute sulphuric acid medium. Furthermore, the stainless steel has good cold and hot forming performance and can be used for replacing expensive nickel base alloy in some harsh environments.
Description
Technical field
The present invention relates to a kind of stainless steel and manufacture method thereof, be meant a kind of at reductants such as dilute sulphuric acids and contain high-alloy stainless steel and the manufacture method of using in the higher halide-ions environment thereof especially.
Background technology
Vitriolic corrodibility is very complicated, and its corrodibility can change with factors vary such as concentration, temperature and impurity.Sulfuric acid presents oxidisability and reductibility because of its concentration is different, it is generally acknowledged that sulfuric acid concentration is lower than at 85% o'clock and is reductibility, although this not enough science also will be lower than 85% sulfuric acid and be called dilute sulphuric acid usually.Dilute sulphuric acid is a reductive acid, so its corrosive property is that cathodic process mainly is the hydrogen depolarization process.Following formula can be arranged:
Anodic process: M → M
N++ ne cathodic process: 2H
++ 2e → H
2
In dilute sulphuric acid, temperature is fairly obvious to effect of metal corrosion.With the rising of temperature, hydrogen overpotential reduces, and promptly temperature raises, the hydrogen evolution corrosion aggravation.
Another corrosive factor that influences dilute sulphuric acid is an impurity, (Fe when containing oxidative impurities
3+, Cu
2+Deng), can reduce the corrodibility of dilute sulphuric acid; And when containing reducing impurity (Cl
-, F
-Deng), not only can aggravate the uniform corrosion of dilute sulphuric acid to metal, also can cause stainless local corrosion (spot corrosion, crevice corrosion, stress corrosion) in addition.
At present, in the Production Flow Chart of many important chemical industry department, all can be applied to the dilute sulphuric acid medium.Most medium is not pure dilute sulphuric acid, and does not generally work at normal temperatures, takes engineerings such as acid recovery as hydrometallurgy, flue gas desulfurization, titanium dioxide.The employed heat-eliminating medium of condenser, interchanger in many in addition Chemical Manufacture flow processs is for containing Cl
-Water or even seawater.Under some situation, the corrodibility harshness very that can become.Common 304 type stainless steels are not useable for the dilute sulphuric acid medium, and 316 type stainless steels only can be used for normal temperature, and concentration is lower than 20% dilute sulphuric acid medium, works as Cl
-When content was 200ppm, 316 can only be used for the normal temperature state, the sulfuric acid below 2%.At room temperature, high-alloy stainless steel 904L can be applicable to the dilute sulphuric acid of any concentration.904L use temperature in 10% bright sulfur acid can reach more than 80 ℃, but when containing 200ppmCl
-The time, but can only use below 40 ℃.Certainly as the higher and Cl of temperature
-In the higher dilute sulphuric acid of content, adopt nickel-base alloy (as C276 etc.), can meet the demands, but cost is too high.Therefore provide a kind of stainless steel that can in these severe rugged environments, use, and its cost is lower than nickel-base alloy again, has very important realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of energy to satisfy the high-alloy stainless steel that contains assorted dilute sulphuric acid medium service requirements, and the cold and hot formability of this stainless steel is good, and what can replace the high nickel-base alloy of price in some rigorous environment novel contains assorted dilute sulphuric acid medium with high-alloy stainless steel and working method thereof.
Realize above-mentioned purpose, the present invention adopts following technical scheme, a kind of dilute sulphuric acid medium high-alloy stainless steel of mixing that contains, it is characterized in that: include chromium, nickel, molybdenum, copper, nitrogen, rare earth and ferrous components, wherein the content of each composition is chromium 19-21% by mass percentage, nickel 18-26%, molybdenum 6-7%, copper 0.5-1.5%, nitrogen 0.15-0.3%, rare earth 0.005-0.04%, surplus is an iron.
In such scheme, chromium metal is the most basic alloying element that stainless steel obtains corrosion resisting property, chromium thermodynamic instability but passivation easily, and chromium and ferrous alloy composition sosoloid can make ferrous alloy have the anti-corrosion characteristics of passivation.It mainly is Cr that stainless passive film is formed
2O
3Or CrOOH, therefore an amount of chromium alloying helps alloy passivation and corrosion proof raising.In the dilute sulphuric acid of reductibility, it is more obvious that chromium and nickel, molybdenum and copper are used effect.Nickel is the thermodynamic instability element, can passivation but passivation ability not as chromium.The corrosion potential of iron nickel alloy moves to positive dirction with the increase of nickel content.Solidity to corrosion all improves with the increase of nickel content in the nitric acid of sulfuric acid, hydrochloric acid and the oxidisability of reductibility.Illustrate that nickel can improve the thermodynamic stability of ferrous alloy.On the other hand, nickel is that austenite former can enlarge the austenitic area strongly, can improve the technology and the mechanical property of alloy.Metal molybdenum is stainless steel and various non-corrosive metal alloy element commonly used, and molybdenum can promote the passivation of alloy and passivation again, reduces the blunt electric current that causes of alloy.It can make stainless steel surface form the oxide film of rich molybdenum, and this oxide film is difficult for dissolving in reductant, so molybdenum can improve alloy reducing resistance medium ability, and can effectively suppress the spot corrosion that chlorion causes.These effects of molybdenum are to produce having under the prerequisite of chromium, and super stainless steel of the present invention has higher chromium, has effectively brought into play the compound action of chromium and molybdenum.Metallic copper is a stainless steel alloy element commonly used, and copper can improve stainless corrosion resistance to sulfuric acid, and the electropotential of copper can suppress hydrogen evolution corrosion than hydrogen height.Being used of copper and molybdenum can be suppressed the dissolving of passive film, and the copper content in the stainless steel can be up to 3.Elemental nitrogen is the new alloy method that grew up in 20th century, is the intensive austenite former.Solubleness can reach 0.4 in austenite, nitrogen be cheap and the element that substitutes effectively nickel (0.1N can be for 2.3～3.0Ni).The solution strengthening of nitrogen can improve the intensity of steel; Nitrogen can improve Corrosion Resistance of Stainless Steels, especially anti-spot corrosion and crevice corrosion behavior; Nitrogen can effectively suppress carbide and intermetallic phase when separating out in this external high-alloy stainless steel, improves processing performances such as welding.The rare earth treatment high-alloy stainless steel starts from U.S. Carpenter company, and rare earth element alloyization is used widely.The form and the desulfating and deoxidation of rare earth may command sulfide improve the mechanical property of steel.Rare earth plays the effect of microalloying.But the poly-partially crystal grain thinning of crystal boundary in the rare earth atom.Rare earth is little in the solubleness of steel, must strict control add-on.Be equipped with copper, nitrogen and rare earth in addition and replenish alloying, make it have very strong anti-dilute sulphuric acid corrosive nature and anti-local corrosion performance, have favorable mechanical performance and cold and hot working performance, can in the dilute sulphuric acid medium, substitute nickel-base alloy.
The further setting of product of the present invention is: also include carbon, boron, sulphur, silicon and manganese, wherein by mass percentage the content of each composition be carbon smaller or equal to 0.03%, boron smaller or equal to 0.03%, sulphur smaller or equal to 0.01%, silicon smaller or equal to 1.5% and manganese smaller or equal to 1.5%.
The technical scheme that method of the present invention adopts is: a kind of working method that contains assorted dilute sulphuric acid medium with high-alloy stainless steel, it is characterized in that: described stainless hot-work can be adopted and forge or rolling form, wherein the forging deformation temperature is 1150～1200 ℃, final forging temperature is 950～1050 ℃, start rolling temperature is 1100～1200 ℃, and finishing temperature is 900～1000 ℃.
The further technical scheme of method is: described stainless solid solution temperature is 1100～1200 ℃, and the time is 15～25 minutes.
Below in conjunction with accompanying drawing the present invention is further described.
Description of drawings
Fig. 1 be the embodiment of the invention and 904L and 316L etc. corrosion curve.
Embodiment
Embodiment one
A kind of dilute sulphuric acid medium high-alloy stainless steel of mixing that contains of the present invention, described high-alloy stainless steel is equipped with suitable proportion based on Gao Ge, nickel, molybdenum, the effect of performance composite alloying.Be equipped with copper, nitrogen, the additional alloying of rare earth on this basis again.Wherein each chemical ingredients according to weight percent is: carbon 0.023; Silicon 1.18; Manganese 1.34; Phosphorus 0.019; Sulphur 0.010; Chromium 19.68; Nickel 19.41; Molybdenum 6.12; Copper 0.67; Nitrogen 0.20, rare earth 0.03; Yu Weitie.The present invention smelts and adopts induction furnace and the refining of secondary esr, and the forging deformation temperature is 1150～1200 ℃, and final forging temperature is 1000 ℃, and start rolling temperature is 1150 ℃, and finishing temperature is 950 ℃, and solid solution temperature is 1150 ℃, solid solution 20 minutes.Table 1, table 2 are respectively the mechanical properties that adopts the different heat treatment mode to be obtained.
Forging deformation temperature of the present invention is 1030 ℃, and the mechanical property of the cold rolled sheet of handling in 8 minutes sees Table 1.
Table 1 is the mechanical property of the embodiment of the invention
| Sample | The sampling direction | Yield strength (MPa) | Tensile strength (MPa) | Unit elongation (δ %) |
| 1-1 | Laterally | 560 | 865 | 21.5 |
| 1-2 | Laterally | 565 | 860 | 25.0 |
| 1-3 | Laterally | —— | 850 | 15.0 |
| 1-4 | Laterally | 490 | 855 | 12.5 |
| 2-1 | Vertically | —— | 880 | 21.0 |
| 2-2 | Vertically | 540 | 875 | 20.0 |
| 2-3 | Vertically | 510 | 815 | 7.0 |
| 2-4 | Vertically | 555 | 865 | 25.0 |
Forging deformation temperature of the present invention is 1150 ℃, the mechanical property such as the table 2 of the cold rolled sheet of handling in 20 minutes.
Table 2 is the mechanical property of the embodiment of the invention
| Sample | The sampling direction | Yield strength (MPa) | Tensile strength (MPa) | Unit elongation (δ %) |
| 3-1 | Laterally | 405 | 730 | 55.0 |
| 3-2 | Laterally | 380 | 695 | 51.0 |
| 3-3 | Laterally | 400 | 715 | 49.0 |
| 3-4 | Laterally | —— | 670 | 49.0 |
| 4-1 | Vertically | 400 | 705 | 39.0 |
| 4-2 | Vertically | 400 | 735 | 43.5 |
| 4-3 | Vertically | 385 | 720 | 42.5 |
| 4-4 | Vertically | 415 | 755 | 40.0 |
Embodiment two
Fig. 1 is seen in the embodiment of the invention and 904L type steel alloy, the corrosion proof contrast of 316L type steel alloy in containing assorted sulfuric acid, and its chemical ingredients sees Table 3.
The chemical ingredients of table 3 embodiment of the invention and compared steel
| Steel grade | C | Si | Mn | Cr | Ni | Mo | Cu | N | Re | Fe |
| Embodiment | 0.023 | 1.18 | 1.34 | 19.68 | 19.41 | 6.12 | 0.67 | 0.20 | 0.03 | Surplus |
| 904L | 0.01 | 0.31 | 1.64 | 20.23 | 23.72 | 4.14 | 1.51 | - | - | Surplus |
| 316L | 0.015 | 0.38 | 0.72 | 16.69 | 10.18 | 2.06 | 0.72 | - | - | Surplus |
Comprehensive accompanying drawing 1 and table 3 can be clear and definite the corrosion resistance nature of the steel alloy that draws the embodiment of the invention better than traditional.
Embodiment three
High-alloy stainless steel of the present invention has good anti-dilute sulphuric acid corrosion and resisting chloride ion penetration, fluorion ability.During the high-alloy stainless steel design, guarantee enough chromium-nickel content, simultaneously with high molybdenum (〉 6%) alloying, and with copper, nitrogen, the additional alloying of rare earth, so very stable in the dilute sulphuric acid of chlorion.Even in the very high dilute sulphuric acid of chlorion (Cl
-Up to 10000ppm), still have good corrosion resisting property, see Table 4.High-alloy stainless steel also is anti-corrosion in the dilute sulphuric acid of fluoride ion and fluoride ion and chlorion, sees Table 5.
The corrosion speed (mm/a) of table 4 high-alloy stainless steel cold rolled sheet in the chloride ion-containing dilute sulphuric acid
The corrosion speed (mm/a) of table 5 high-alloy stainless steel in the dilute sulphuric acid of fluoride ion and fluorine-containing and chlorion
| %H 2SO 4 | 10 | 15 | 20 | 30 | 50 |
| 1.0%F - | 0.03761 | 0.04653 | 0.03233 | 0.03231 | 0.02831 |
| 1.0%F -+0.5%Cl - | —— | 0.06930 | —— | 0.03611 | —— |
High-alloy stainless steel of the present invention belongs to high chromium-stainless steel, adopts high molybdenum (〉 6%Mo simultaneously) alloying, and added anti-spot corrosion elemental nitrogen.By spot corrosion exponential experimental formula: PRE=%Cr+3.3%Mo+16%N, calculation result shows that the spot corrosion index of this high-alloy stainless steel can reach 45.The stainless spot corrosion index of 904L type is 36 by contrast, and the spot corrosion index of Sanicro28 is 39.As seen this high-alloy stainless steel has very strong pitting corrosion resistant performance.(15% H at 80 ℃
2SO
4+ 0.2%Cl
-), (15% H
2SO
4+ 0.5%Cl
-), (15% H
2SO
4+ 1.0%F
-) after the spot corrosion experiment in the medium, observe by SEM and not find point corrosion pit.Show that high-alloy stainless steel of the present invention has than the anti-spot corrosion of intensity and anti-fluorine, chlorion ability.
With reference to the regulation of GB/T17898-1999, specimen size is 0.9 * 15 * 75, the side polishing.On universal testing machine, sample is bent to the U type with the 10mm pressure head.Adopt the tetrafluoroethylene screw to exert pressure then.Respectively at 80 ℃ (15% H
2SO
4+ 0.2%Cl
-), (15% H
2SO
4+ 0.5%Cl
-), (15% H
2SO
4+ 1.0%F
-) experimentize in the medium.The result shows that the high-alloy stainless steel cold rolled sheet does not produce stress corrosion crack (SCC).
Claims (4)
1. one kind contains assorted dilute sulphuric acid medium high-alloy stainless steel, it is characterized in that: include chromium, nickel, molybdenum, copper, nitrogen, rare earth and ferrous components, wherein the content of each composition is chromium 19-21% by mass percentage, nickel 18-26%, molybdenum 6-7%, copper 0.5-1.5%, nitrogen 0.15-0.3%, rare earth 0.005-0.04%, surplus is an iron.
2. by the described dilute sulphuric acid medium high-alloy stainless steel of mixing that contains of claim 1, it is characterized in that: also include carbon, boron, sulphur, silicon and manganese, wherein by mass percentage the content of each composition be carbon smaller or equal to 0.03%, boron smaller or equal to 0.03%, sulphur smaller or equal to 0.01%, silicon smaller or equal to 1.5% and manganese smaller or equal to 1.5%.
3. one kind contains the working method that assorted dilute sulphuric acid medium is used high-alloy stainless steel, it is characterized in that: described stainless hot-work can be adopted and forge or rolling form, wherein the forging deformation temperature is 1150～1200 ℃, final forging temperature is 950～1050 ℃, start rolling temperature is 1100～1200 ℃, and finishing temperature is 900～1000 ℃.
4. by the described working method that contains assorted dilute sulphuric acid medium with high-alloy stainless steel of claim 3, it is characterized in that: described stainless solid solution temperature is 1100～1200 ℃, and the time is 15～25 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131961A (en) * | 2013-03-08 | 2013-06-05 | 宣达实业集团有限公司 | Corrosion-resistant stainless steel plate, and preparation method and application thereof |
| CN103725987A (en) * | 2013-11-28 | 2014-04-16 | 旅顺华通耐腐蚀泵配件厂 | Highly corrosion-resistant and abrasion-resistant alloy steel in thiamine mother liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57171651A (en) * | 1981-04-15 | 1982-10-22 | Nisshin Steel Co Ltd | Perfect austenite stainless steel with superior corrosion resistance at weld zone |
| US20100183475A1 (en) * | 2009-01-21 | 2010-07-22 | Roman Radon | Chromium manganese - nitrogen bearing stainless alloy having excellent thermal neutron absorption ability |
| CN101935809A (en) * | 2010-09-10 | 2011-01-05 | 钢铁研究总院 | High performance rare-earth duplex stainless steel alloy material and preparation method thereof |
-
2011
- 2011-05-24 CN CN 201110134627 patent/CN102212758A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57171651A (en) * | 1981-04-15 | 1982-10-22 | Nisshin Steel Co Ltd | Perfect austenite stainless steel with superior corrosion resistance at weld zone |
| US20100183475A1 (en) * | 2009-01-21 | 2010-07-22 | Roman Radon | Chromium manganese - nitrogen bearing stainless alloy having excellent thermal neutron absorption ability |
| CN101935809A (en) * | 2010-09-10 | 2011-01-05 | 钢铁研究总院 | High performance rare-earth duplex stainless steel alloy material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131961A (en) * | 2013-03-08 | 2013-06-05 | 宣达实业集团有限公司 | Corrosion-resistant stainless steel plate, and preparation method and application thereof |
| CN103131961B (en) * | 2013-03-08 | 2015-09-09 | 宣达实业集团有限公司 | A kind of corrosion-resistant stainless steel plate and preparation method thereof and application |
| CN103725987A (en) * | 2013-11-28 | 2014-04-16 | 旅顺华通耐腐蚀泵配件厂 | Highly corrosion-resistant and abrasion-resistant alloy steel in thiamine mother liquor |
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Application publication date: 20111012 |