CN103160753A - Zr-containing sulphuric acid dew point corrosion resistant steel plate and manufacturing method thereof - Google Patents
Zr-containing sulphuric acid dew point corrosion resistant steel plate and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a Zr-containing sulphuric acid dew point corrosion resistant steel plate and a manufacturing method thereof. The steel plate comprises the following components: 0.02%-0.15% C, 0.15%-0.55% of Si, 0.50%-1.60% of Mn, less than or equal to 0.020% of P, less than or equal to 0.020% of S, 0.08%-0.30% of Ni, 0.20%-0.60% of Cu, 0.30%-1.50% of Cr, 0.04%-0.30% of Sb, 0.01%-0.05% of Zr, 0.015%-0.045% of Als, less than or equal to 0.07% of Nb, 0.01%-0.05% of Ti, and the balance Fe and unavoidable impurities. The manufacturing method includes the smelting and rolling, and the method is characterized in that the heating temperature of a steel billet is 1190-1230DEG C, the rolling temperature is 1070-850DEG C, a last pass reduction amount is greater than or equal to 30%, the cooling rate of a two-phase region is 10-15DEG C/s, a final cooling temperature is 660-550DEG C, and air cooling is carried out after rolling. The type of steel provided in the invention has good corrosion resistance and good welding performance in an acidic gas corrosion environment, and has a simple manufacturing process, thus being especially suitable for equipment easy to undergo acid corrosion in petroleum, coal chemical industry, electric power and other industries, delivery pipelines, as well as chimneys.
Description
Technical field
The invention belongs to technical field of ferrous metallurgy, relate in particular to a kind of Zr of containing corrosionproof steel against sulfuric acid at dew point plate and manufacture method thereof.
Background technology
Sour gas corrosion is the most general a kind of erosional forms that runs in the industries such as oil, chemical industry, electric power, both can form uniform corrosion to equipment and also can form local corrosion.Sulfuric acid dew point corrosion resistant generally appears at boiler preheater and economizes gas fittings, and on transport pipe and chimney.All contain a large amount of sulphur (S) in the fuel that boiler is used such as heavy oil and coal, become sulfurous gas (SO through combustion decomposition
2) and sulphur trioxide (SO
3), be combined with water vapor in dew-point temperature and become sulfuric acid (H
2SO
4) by rare thickening, equipment there is strong corrosive nature.SO
2Can cause the acidification of metallic surface thin liquid film, its existence can cause the booster action of corrosion product autocatalysis.
Steel for resisting sulfuric acid dew point corrosion is a kind of not only sulfuric acid dew point corrosion resistant but also atmospheric corrosion resistance steel grade.The corrosionproof steel against sulfuric acid at dew point design of alloy is after the weathering steel of being born in the U.S. in 1933, to the condense research of phenomenon of sulphuric acid dew point, the CORTEN steel that discovery contains the alloying elements such as certain C u, P, Cr, Ni has certain solidity to corrosion, as the beginning, this low alloy steel is begun to be applied to first the air preheater of boiler.Initial find to add in steel 0.2%～0.5% copper and can greatly improve steel to the solidity to corrosion of various concentration sulfuric acid, copper becomes one of basal component of corrosionproof steel against sulfuric acid at dew point.
The corrosionproof steel against sulfuric acid at dew point of Japan exploitation mainly is divided into two classes according to environment for use: (1) take 0.2%～0.5%Cu,＞0010%S is as matrix, adds a small amount of Sn and Sb element, its compound becomes the inhibitor that hydrogen is reacted; (2) for the IV corrosive environment of high temperature, high-concentration sulfuric acid, and Cu, the Cr of CORTEN steel homologous ray or Cu, Cr, Ni as foundational development.As described in examined patent publication 43-14585 communique, compound interpolation Cu, Sb have corrosion resistance to sulfuric acid dew point and are used confirmation.
Domestic development and exploitation for corrosionproof steel against sulfuric acid at dew point started late, the steel grade of composition system and the general Japanese of Application standard, the B485NL of In Baosteel, the 10CrlCu of Anshan iron and steel plant are wherein typically arranged, in addition the NS corrosionproof steel against sulfuric acid at dew point product of the ND of Jiangyin special steel (09CuCrSb) steel, the Ji 12MnCuCr of steel and Baosteel one steel company.
The B485NL of the CORTEN steel of the U.S. and domestic In Baosteel, the 10CrlCu of Anshan iron and steel plant, the 12MnCuCr of Ji steel is that Cr, Cu are steel (publication number: 90101258.0), but omitted the good element S n of anti-sulphuric acid dew point and Sb in Cr, the design of Cu set member, its solidity to corrosion is unsatisfactory in sour environment.
As mentioned above, the desired steel plate that has good corrosion resistance nature and good welds performance at the sour gas corrosion environment.Now also there is no production technology preferably.
Summary of the invention
The object of the invention is to overcome the existing deficiency of prior art, a kind of steel plate and manufacture method thereof that has good corrosion resistance nature and good welds performance under the sour gas corrosion environment is provided.
The present invention is achieved in that this moiety weight percent (Wt%) that contains Zr corrosionproof steel against sulfuric acid at dew point plate is: C:0.02%～0.15%, Si:0.15%～0.55%, Mn:0.50%～1.60%, P :≤0.020%, S :≤0.020%, Ni:0.08%～0.30%, Cu:0.20%～0.60%, Cr:0.30%～1.50%, Sb:0.04%～0.30%, Zr:0.01%～0.05%, Als:0.015%～0.045%, Nb :≤0.07%, Ti:0.01%～0.05%, surplus are Fe and inevitable impurity.
The present invention adds Zr in alloy, Zr is a strong oxide compound, strong nitride forming element. and its compound not only fusing point is high (as ZrO
2Fusing point is 2677 ℃, and the ZrN fusing point is 3255 ℃), hardness is also high, can suppress Austenite Grain Growth in steel, and the ferrite in steel is also fine ferrite grain.Grain refining can improve the homogeneity of corrosion, and is particularly favourable to anti-local corrosion.The corrosion resistance nature of Zr also depends on their dense oxidation film ZrO
2And the passivation behavior in corrosive medium, the passive potential region of Zr is little, and the transpassivation phenomenon is arranged, thereby has the sulfuric acid dew point corrosion resistant of raising ability; The Zr element can effectively promote acicular ferrite to form, and improves significantly the toughness of weld seam.
Composition Design of the present invention be the reasons are as follows:
One of important feature of the present invention is the selection of C element, and it be strengthening element that the carbon content maximum should not surpass 0.30%, C element, and carbon content is on the low side will damage the intensity of material, and the selection carbon content is 0.02%～0.15%.Reduce carbon content, be conducive to improve on the one hand toughness, can significantly improve the Plate Welding performance simultaneously.
Si strengthening element, solid solution improve the yield strength of steel in ferrite, lower than 0.15%, can increase the steel making working procedure cost.Higher than 0.50%, easily make slab produce the regeneration iron sheet that is difficult to remove in this composition combination, affect the surface quality of finished steel plate.Therefore determine that its scope is 0.15%～0.55%.
Mn mainly is dissolved in ferrite and plays strengthening effect, improves the hardening capacity of steel, is again the element that certainly exists when smelting in steel.Determine its content range according to the intensity rank level that will reach, but high lower than 0.15% pair of smelting requirements, increasing cost, content too Gao Shiyi causes segregation, determines that therefore its scope is 0.50～1.60%.
P is easy to cause segregation, and is unfavorable to weldability and processability.For guaranteeing weldability and processability requirement, the present invention controls it lower than 0.020%.
S is harmful element, on mechanical property, is more low better naturally, but too low meeting causes process cost to increase, and the present invention controls it lower than 0.020%.
Ni is precious metal element, improves the hardening capacity element, improves the intensity of steel and does not reduce its toughness, and its scope that plays obvious corrosion-resistant effect is more than 1.0%, and when suitably adding this element mainly also can take precautions against heating of plate blank, surface C u splits phenomenon.For controlling cost, limiting its scope is 0.08～0.30%.
Cu has good result for improving solidity to corrosion, and necessary content is 0.20%, but content surpasses 0.60%, and its effect reaches capacity, and therefore limiting its scope is 0.20%～0.60%.
Cr improves the hardening capacity element strongly, and carbide is used in conjunction with Cu the solidity to corrosion that improves steel, and necessary amount is 0.30%, and therefore limiting its content range is 0.30～1.50%.
Sb improves the solidity to corrosion effective element, and it forms the dense oxidation film that is rich in the elements such as Sb, Zr, Cu, Cr higher than several times of matrixes of one deck densification on the surface, thereby has high sulfuric-resisting dew point corrosion corrosive power; There is no effect lower than 0.04%, owing to there being the hot-work deterioration, so its content is advisable between 0.04%～0.30% greater than 0.30%.
The nitrogen killer that Als is traditional, forming AlN can refine austenite crystal grain, and therefore limiting its content range is 0.015%～0.045%.
The strong carbonitride forming element of Zr forms ZrN, ZrC and all can stop Austenite Grain Growth in soaking with in reheating process, and refine austenite crystal grain is even deformation also can obtain superfine crystal particle under the high temperature austenite recrystallization zone.Also can control form, the raising transverse impact toughness of sulfide, improve the welding property of steel.The erosion rate of nanometer-size die size is lower than the erosion rate of common crystal grain, along with the erosion rate that reduces of nanocrystalline grain size also reduces.The Zr corrosion resistance nature depends on their oxide film ZrO2, and the passivation behavior in corrosive medium.The oxide compound of Zr forms than the oxide compound of Ti can be lower, that is more can the refinement coarse-grain tissue of heat affected zone.The Zr element can effectively promote acicular ferrite to form, and improves significantly the toughness of weld seam.The content range of Zr should be limited to 0.010%～0.050%.
The strong carbonitride forming element of Ti forms TiN, TiC and all can stop Austenite Grain Growth in soaking with in reheating process, refine austenite crystal grain.The Ti content range should be limited to 0.010%～0.050%.
Can postpone austenite recrystallization during the Nb hot rolling and reach the purpose of crystal grain thinning, in cooling and course of hot rolling subsequently, the NbCN disperse educt plays the precipitation strength effect, improves intensity.In reheating process, stop Austenite Grain Growth.When reaching 0.07% due to Nb content, Grain refinement reaches capacity.Be 0.07% so limit its upper content limit.
The manufacture method that the present invention contains Zr corrosionproof steel against sulfuric acid at dew point plate comprises smelting and rolling, the Heating temperature that is characterized in steel billet is 1210 ± 20 ℃, be rolled in austenite recrystallization district and non-recrystallization zone, the excess Temperature energy consumption raises, and the oxidational losses of steel billet is large; Start rolling temperature is limited to below 1070 ℃, and the plasticity of steel is good, and intensity is low, is easy to rollingly, and base can not cause size bad and the shape defects such as nose, wooden dipper song occur affect normally carrying out of operation of lower step because of the temperature difference end to end; Finishing temperature is greater than 850 ℃, but finishing temperature is higher than 950 ℃, and grain refining is not enough, affects strengthening effect, and lower than 850 ℃, the load of milling train can increase, and the transverse and longitudinal poor performance mutation of steel plate is large; Rolling final pass draught 〉=30%; Carry out suitable water spray acceleration at 850～700 ℃ of two-phase regions cooling, speed of cooling is 10～15 ℃/s, and 660～550 ℃ of final cooling temperatures, final cooling temperature form crystal grain and substantially do not grow up, but too low temperature are difficult to curling for roll bending lower than 660 ℃; Roll laggard line space cold.
Steel grade of the present invention has good corrosion resistance nature and good welding property under the sour gas corrosion environment, and manufacturing process is simple, this steel grade is specially adapted to the industries such as oil, Coal Chemical Industry, electric power and is prone to the boiler preheater of acid attack and economizes gas fittings, and on transport pipe and chimney.
Embodiment
The present invention is further illustrated below by embodiment.
The embodiment of the present invention is smelted with rolling at use for laboratory 80kg according to the component proportion of technical scheme.The chemical composition of steel grade of the present invention sees Table 1.The chemical composition of embodiment of the present invention steel sees Table 2.The rolling technology of embodiment of the present invention steel sees Table 3.The performance of embodiment of the present invention steel sees Table 4.
The chemical composition of table 1 steel grade of the present invention (wt%)
The chemical composition (wt%) of table 2 embodiment of the present invention steel
| C | Si | Mn | P | S | Cu | Cr | Ni | Als | Sb | Nb | Ti | Zr | |
| Comparative Examples 1 | 0.10 | 0.30 | 0.85 | 0.010 | 0.006 | 0.25 | 0.65 | - | - | - | - | - | - |
| Comparative Examples 2 | 0.09 | 0.25 | 0.54 | 0.015 | 0.004 | 0.26 | 0.95 | 0.46 | - | 0.05 | - | - | - |
| Embodiment 1 | 0.08 | 0.35 | 127 | 0.009 | 0.009 | 0.38 | 0.85 | 0.17 | 0.015 | 0.09 | 0.015 | 0.021 | 0.011 |
| Embodiment 2 | 0.14 | 0.20 | 0.53 | 0.008 | 0.005 | 0.22 | 0.35 | 0.09 | 0.030 | 0.05 | 0.028 | 0.022 | 0.025 |
| Embodiment 3 | 0.04 | 0.19 | 0.99 | 0.007 | 0.008 | 0.55 | 1.45 | 0.15 | 0.018 | 0.19 | 0.065 | 0.020 | 0.015 |
| Embodiment 4 | 0.10 | 0.25 | 0.78 | 0.011 | 0.007 | 0.25 | 0.89 | 0.18 | 0.043 | 0.15 | - | 0.045 | 0.011 |
| Embodiment 5 | 0.07 | 0.38 | 149 | 0.016 | 0.005 | 0.26 | 120 | 0.30 | 0.023 | 0.29 | - | 0.031 | 0.020 |
| Embodiment 6 | 0.08 | 0.21 | 122 | 0.009 | 0.006 | 0.26 | 125 | 0.25 | 0.034 | 0.22 | - | 0.026 | 0.012 |
| Embodiment 7 | 0.12 | 0.52 | 0.89 | 0.018 | 0.003 | 0.26 | 0.40 | 0.12 | 0.025 | 0.07 | - | 0.012 | 0.029 |
The rolling technology of table 3 embodiment of the present invention steel
| Heating temperature ℃ | Start rolling temperature ℃ | Finishing temperature ℃ | Final cooling temperature ℃ | |
| Embodiment 1 | 1210 | ＜1070 | 855 | 645 |
| Embodiment 2 | 1220 | ＜1070 | 875 | 650 |
| Embodiment 3 | 1225 | ＜1070 | 850 | 580 |
| Embodiment 4 | 1200 | ＜1070 | 890 | 660 |
| Embodiment 5 | 1230 | ＜1070 | 865 | 605 |
| Embodiment 6 | 1225 | ＜1070 | 860 | 620 |
| Embodiment 7 | 1195 | ＜1070 | 850 | 625 |
The performance of table 4 embodiment of the present invention steel
| Rel(MPa) | Rm(MPa) | A(％) | 20 ℃, 20%H2SO4 solution, erosion rate (g/m 2h) | |
| Comparative Examples 1 | 385 | 542 | 25.6 | 25.0 |
| Comparative Examples 2 | 320 | 430 | 38.0 | 11.4 |
| Embodiment 1 | 385 | 530 | 31.0 | 8.58 |
| Embodiment 2 | 370 | 490 | 34.0 | 7.31 |
| Embodiment 3 | 450 | 595 | 26.5 | 4.61 |
| Embodiment 4 | 420 | 580 | 32.0 | 8.49 |
| Embodiment 5 | 400 | 525 | 29.0 | 4.98 |
| Embodiment 6 | 385 | 535 | 27.5 | 6.58 |
| Embodiment 7 | 370 | 500 | 29.5 | 9.05 |
Claims (2)
1. one kind contains Zr corrosionproof steel against sulfuric acid at dew point plate, the moiety weight percent that it is characterized in that steel plate is: C:0.02%～0.15%, Si:0.15%～0.55%, Mn:0.50%～1.60%, P :≤0.020%, S :≤0.020%, Ni:0.08%～0.30%, Cu:0.20%～0.60%, Cr:0.30%～1.50%, Sb:0.04%～0.30%, Zr:0.01%～0.05%, Als:0.015%～0.045%, Nb :≤0.07%, Ti:0.01%～0.05%, surplus are Fe and inevitable impurity.
2. described manufacture method that contains Zr corrosionproof steel against sulfuric acid at dew point plate of claim 1, comprise smelting and rolling, the Heating temperature that it is characterized in that steel billet is 1210 ± 20 ℃, 1070～850 ℃ of rolling temperatures, final pass draught 〉=30%, two-phase region accelerates cooling, 10～15 ℃/s of speed of cooling, 660～550 ℃ of final cooling temperatures roll rear air cooling.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589972A (en) * | 2013-10-10 | 2014-02-19 | 中天钢铁集团有限公司 | Low-cost low alloy steel for resistance to dew point corrosion of sulfuric acid as well as production process and application of low alloy steel |
| CN106435129A (en) * | 2016-06-30 | 2017-02-22 | 宝钢不锈钢有限公司 | Ferrite stainless steel with good toughness and good corrosion resistance, and manufacturing method thereof |
| CN106521317A (en) * | 2016-11-18 | 2017-03-22 | 东北大学 | Manufacturing method for low-carbon thin strip steel containing acicular ferrite |
| CN111088463A (en) * | 2020-01-21 | 2020-05-01 | 鞍钢股份有限公司 | Steel bar resistant to corrosion in low-temperature atmospheric environment and production method thereof |
| JP2021017636A (en) * | 2019-07-23 | 2021-02-15 | 日本製鉄株式会社 | Steel |
| CN112760567A (en) * | 2020-12-25 | 2021-05-07 | 鞍钢股份有限公司 | Steel plate with excellent toughness for high-speed train bogie and manufacturing method thereof |
| CN112779478A (en) * | 2020-12-25 | 2021-05-11 | 鞍钢股份有限公司 | Weather-resistant steel plate for 390 MPa-grade high-speed train bogie and manufacturing method thereof |
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| CN103589972A (en) * | 2013-10-10 | 2014-02-19 | 中天钢铁集团有限公司 | Low-cost low alloy steel for resistance to dew point corrosion of sulfuric acid as well as production process and application of low alloy steel |
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| CN106435129A (en) * | 2016-06-30 | 2017-02-22 | 宝钢不锈钢有限公司 | Ferrite stainless steel with good toughness and good corrosion resistance, and manufacturing method thereof |
| CN106435129B (en) * | 2016-06-30 | 2021-04-02 | 宝钢德盛不锈钢有限公司 | Ferritic stainless steel with good toughness and corrosion resistance and manufacturing method thereof |
| CN106521317A (en) * | 2016-11-18 | 2017-03-22 | 东北大学 | Manufacturing method for low-carbon thin strip steel containing acicular ferrite |
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| JP2021017636A (en) * | 2019-07-23 | 2021-02-15 | 日本製鉄株式会社 | Steel |
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| CN111088463A (en) * | 2020-01-21 | 2020-05-01 | 鞍钢股份有限公司 | Steel bar resistant to corrosion in low-temperature atmospheric environment and production method thereof |
| CN111088463B (en) * | 2020-01-21 | 2021-04-27 | 鞍钢股份有限公司 | Steel bar resistant to corrosion in low-temperature atmospheric environment and production method thereof |
| CN112760567A (en) * | 2020-12-25 | 2021-05-07 | 鞍钢股份有限公司 | Steel plate with excellent toughness for high-speed train bogie and manufacturing method thereof |
| CN112779478A (en) * | 2020-12-25 | 2021-05-11 | 鞍钢股份有限公司 | Weather-resistant steel plate for 390 MPa-grade high-speed train bogie and manufacturing method thereof |
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