CN101892439A - Sulfuric acid dew point corrosion resistant steel - Google Patents
Sulfuric acid dew point corrosion resistant steel Download PDFInfo
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- CN101892439A CN101892439A CN2009100277687A CN200910027768A CN101892439A CN 101892439 A CN101892439 A CN 101892439A CN 2009100277687 A CN2009100277687 A CN 2009100277687A CN 200910027768 A CN200910027768 A CN 200910027768A CN 101892439 A CN101892439 A CN 101892439A
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- acid dew
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Abstract
The invention relates to sulfuric acid dew point corrosion resistant steel, belonging to the technical field of metal materials. The steel comprises the following components by mass: 0.05-0.1% of C, 0.1-0.35% of Si, 0.3-0.8% of Mn, 0-0.02% of P, 0-0.01% of S, 0.5-1.0% of Cr, 0.2-0.5% of Cu, 0.04-0.1% of Sb, 0.01-0.06% of Ti, 0.0004-0.001% of Ca and the balance Fe. The steel obviously improves the acid corrosion resistance under the premise of ensuring mechanical property of the steel, not only resists sulfuric acid dew point corrosion but also resists atmospheric corrosion and has obvious substantial characteristics and prominent progress compared with the prior art.
Description
Technical field
The present invention relates to a kind of acid corrosion-resistant steel, especially a kind of steel for resisting sulfuric acid dew point corrosion belongs to the metallic substance technical field.
Background technology
The sulfuric acid dew point corrosion environment generally appears on boiler preheating device and economizer equipment, air preheater heat exchange element and line of pipes and flue, the chimney.A large amount of examples show: sulfuric acid dew point corrosion can cause great destruction to the device of above-mentioned industry.The effective ways that solve the sulfuric acid dew point corrosion of steel can be by reducing amount and the vitriolic generation that aflame sulphur content suppresses S02 in the flue gas.But be subjected to the restriction of factors such as raw material supply situation, operation possibility and thermo-efficiency, implement difficulty, effect is not remarkable.Or adopt enamel or non-metallic coating can avoid the sulfuric acid dew point corrosion of member to a certain extent, but difficulty of construction is big, influences heat exchange efficiency simultaneously.Optimal scheme is exactly that the ferrous materials of sulfuric acid dew point corrosion environment itself has the characteristic of sulfuric acid dew point corrosion resistant.
According to the documents and materials introduction, in the steel for resisting sulfuric acid dew point corrosion that is using at home at present, mainly contain the S-tenl of Baosteel, the ND steel of the emerging clear special steel in Jiangyin, the JNS steel of Ji steel etc., and applied for Chinese patent (table 1).These steel grades have a common characteristic: the alloying elements such as Cr, Cu that all contain corrosion resistance features, the fine and close corrosion products film that makes steel generate interpolation elements such as being rich in Cu, Cr in corrosion process stops corrosive further to take place, and corrosion potential is moved to passivation region, keep the relatively low electric current of keeping passivation simultaneously.The production steel grades system of each tame steel mill has points of resemblance, but its characteristics are arranged respectively, as publication number is CN1490427A and CN1123845A patent, adopts with Cr-Cu set member prescription and relies on interpolation Sb, Ti element, forms the purpose that the Cu2Sb tunicle reaches sulfuric acid dew point corrosion resistant on the steel grade surface; Publication number is CN 1054802A and CN 1052150A patent, adopts Cu element and S in the steel to react, and forms Cu2S and add Re and the element acting in conjunction of element such as V and adding in corroding rusty scale, reaches the purpose of sulfuric acid dew point corrosion resistant.
Table 1 steel for resisting sulfuric acid dew point corrosion related application and chemical ingredients
Experiment showed, that above-mentioned domestic existing steel for resisting sulfuric acid dew point corrosion is that 30 ℃, concentration are that Q345B compares with General Structural Steel under 20% the sulphuric acid soln immersion corrosion test conditions in temperature, erosion resistance improves between 8～20 times.
Summary of the invention
The objective of the invention is to: on the prior art basis, propose the steel for resisting sulfuric acid dew point corrosion that a kind of corrosion resistance nature further significantly improves.
Studies show that sulfuric acid belongs to non-oxidizing acid, this type of acid is the replacement(metathesis)reaction of metal pair hydrogen to Corrosion of Metallic Materials behavior macro manifestations.Learn the hydrogen evolution corrosion process that may be interpreted as in theory (also claiming the liberation of hydrogen corrosion) from corrosion.With regard to the common used material carbon steel, material all is in the activation corrosion state in the dilute sulphuric acid environment, but mechanism of corrosion is slightly different again.The corrosion of carbon steel in dilute sulphuric acid or other non-oxidizable acid solution belongs to anodic polarization and cathodic polarization mixture control process.This is that hydrogen is also bigger at the overpotential of iron surface evolution reaction simultaneously because the solubilizing reaction activation polarization of iron is bigger, so both play a driving role to corrosion process simultaneously, causes corrosion speed to be accelerated.Therefore, need in ferrous materials, to add corresponding alloying element, in sulfuric acid medium, control process of anodic polarization, produce passivation to a certain degree by these elements, metal ion must penetrate oxide film just can enter solution, so the anodic polarization effect is greater than cathodic polarization.
In order to reach above purpose, the applicant gropes through repetition test on the basis of theory research, and the mass percent that has proposed the various compositions of steel for resisting sulfuric acid dew point corrosion of the present invention is
C:0.05-0.1%, Si:0.1-0.35%, Mn:0.3-0.8%, P:0-0.02%, S:0-0.01%, Cr:0.5-1.0%, Cu:0.2-0.5%, Sb:0.04-0.1%, Ti:0.01-0.06%, Ca:0.0004%-0.001%, surplus is Fe.
Steel for resisting sulfuric acid dew point corrosion of the present invention is a kind of not only sulfuric acid dew point corrosion resistant but also atmospheric corrosion resistance steel grade, because wherein each component composition has following effect:
The Cu element---play a part activated cathode in the atomospheric corrosion process of steel, can promote steel to produce anode passivation under the certain condition, thereby reduce the corrosion speed of steel, the enrichment of Cu in rusty scale can greatly improve the protective value of rusty scale.For reaching the effect of the Cu enrichment in the rusty scale, require Cu＞more than 0.20%.Elements such as the Cu in Cr element and the steel, Si mate, and can significantly improve the corrosion resistance nature of steel.Its minimum content is more than 0.5%, and reason is that the electropotential of chromium is lower, has the effect of passivation tendency, thereby improves corrosion resisting property.
The Sb element---can suppress anodic reaction, simultaneously with steel in the Cu element form Cu on the steel surface
2The Sb tunicle can suppress cathodic reaction, and sulfuric acid dew point corrosion is had the good restraining effect.The adding of Sb element is also to stoping rare H
2SO
4Corrosion play obvious effect.For forming Cu on the steel surface
2The Sb tunicle, requiring the Sb constituent content is the level of 0.04-0.10%.
The Ti element---may make the cycling processability of steel be subjected to certain influence owing to add the Sb element.In steel, add trace amount of titanium, can in steel, form the nitride or the carbide of titanium, can postpone the recrystallize of austenite crystal and the tendency of growing up, thereby improve the performance of steel, especially can effectively improve the welding property of reprocessing.Require the Ti constituent content in 0.010～0.060% scope.
Yet, even add above beneficial element, for guaranteeing the resultant crystallization effect, must forced oxidation.When having oxygen enrichment to exist in the medium, the passive film defective on the metal material surface easily is repaired, thereby erosion rate reduces.But because of having the solid particulate abrasive action in the flue gas simultaneously, its passive film is is easily worn and torn by solid particulate, thereby erosion rate is increased greatly.While is because of the reason of dewfall, the existence of media such as Cl-, NOx-is often arranged in the liquid film of metallic surface, Cl-, NOx-are easily in the oxide film surface adsorption, formation contains Cl-, NOx-ionic surface compound, because this compound lattice imperfection is more, and have bigger solubleness, so can cause the partial fracture of oxide film.In addition, the ion that is adsorbed on electrode surface has the repulsion electronic capability, also impels the ionization of metal, quickens the corrosion of ferrous materials; If behind metallic substance and the sulfuric acid reaction, can produce a kind of settling that is insoluble in the surperficial liquid film and can be deposited on the metallic surface and can play barrier metal and further corroded by surperficial liquid film.For this reason, the present invention is transported to Ca in the molten steel, Ca constituent content＞0.0004% in the control molten steel.Rely on micro-Ca element and effect of sulfuric acid to generate the vitriol (CaSO of infusibility
4) in the metallic surface deposition, make the passive film of metallic surface be easy to be repaired, be more than 25 times of General Structural Steel Q345B thereby make its corrosion resistance nature, significantly improved the corrosion resistance nature of steel for resisting sulfuric acid dew point corrosion of the present invention.
Can think; the present invention is based on the Cu-Cr weather resisting steel; add microalloy elements such as micro-Ca, Ti, Sb, Mn; make ferrous materials that passivation take place when metallic surface sulfuric acid liquid film corrodes; produce protective membrane in the metallic surface; suppress generation and the diffusion of H+ in the surperficial liquid film, play preventing the corrosive purpose.
Evidence, the present invention has significantly improved the acid corrosion-resistant performance under the prerequisite that guarantees acid corrosion-resistant steel mechanical characteristic, both sulfuric acid dew point corrosion resistant, atmospheric corrosion resistance compared with prior art, has significant substantive distinguishing features and outstanding progress again.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment one
The mass percent of the various compositions of the steel for resisting sulfuric acid dew point corrosion of present embodiment (code name BNS440) sees Table 2 NO.1, adopts traditional steel products to manufacture long flow process: blast furnace ironmaking → molten iron pre-desulfurization → converter top bottom blowing → Ar station/or LF stove refining → continuous casting → zero defect continuous casting steel billet → check → heating → breaking down → finish rolling → cool off → batch → the finished product hot-rolled sheet coil.Production control requires: molten iron pre-desulfurization controls to the S element below 0.010%; The converter top bottom blowing carries out the composition adjustment with C, Si, Mn, S, P, through the Ar station/or S is taken off in the refining of LF stove, trimming arrives the control requirement, feeds an amount of iron-calcium line simultaneously and carries out secondary refining, guarantees the purity of molten steel; Continuous casting adopts low-carbon (LC) Copper Bearing Steel privacy protection slag, and whole process is blown Ar protection casting, adopts technicians such as dynamically gently depressing the segregation of technology control steel grades to be cast into the zero defect continuous casting steel billet; After process furnace is heated to 1200 ℃ with slab, rolling on Continuous Heat tandem rolling mill group; Control the key control parameters such as temperature, intermediate blank thickness and width of slab well at the roughing milling train; Finish rolling tandem rolling unit is after recrystallization zone and the controlled rolling of non-recrystallization district, and the finish rolling temperature in requires greater than 1020 ℃, and finishing temperature requires greater than 850 ℃; Require the coiling temperature hit rate more than 97%, control cold injection flow rate and coiling temperature, batching more than 600 ℃.Product thickness is 2.0-12.0mm.
The mechanical property of product sees Table the NO.1 hurdle in 3, Rel 〉=325MPa, and Rm 〉=440MPa, A% 〉=22%, sampling detects corrosion resistance nature and sees Table 4 NO.1 hurdle.As can be seen from Table 4, be 30 ℃ in temperature, concentration is that BNS440 is more than 25 times of erosion resistance of General Structural Steel Q345B under 20% the sulphuric acid soln immersion corrosion test conditions, is erosion resistance 15 times or more of common atmospheric corrosion resistance with steel SAP-H.Domestic steel for resisting sulfuric acid dew point corrosion of the same type is 30 ℃ in temperature, and concentration is that Q345B compares with General Structural Steel under 20% the sulphuric acid soln immersion corrosion test conditions, and erosion resistance is between 8～20 times; And add after the microalloy elements such as Ca, Ti, Sb, compare sulfuric acid corrosion resistant effect highly significant with the sulfuric acid corrosion resistant rate of domestic steel for resisting sulfuric acid dew point corrosion of the same type.
In the above steel-smelting production process control process, preferably adopt and feed the calcium line refinery practice, under the condition of starvation, Ca is transported in the molten steel, avoid its oxidation, Ca constituent content＞0.0004% in the control molten steel.The vitriol (CaSO4) that relies on Ca element and effect of sulfuric acid to generate infusibility deposits in the metallic surface, makes the passive film of metallic surface be easy to be repaired and plays corrosion resistant purpose.
In addition, consider that the element segregation in the alloying constituent will have a strong impact on the corrosion resisting property of corrosionproof steel against sulfuric acid at dew point, even local corrosion can take place.In controlling of production process requires, from the purity that improves steel with prevent that two aspect measures of component segregation from solving; The purity that be to improve steel requires C＜0.10%, and P＜0.020%, S＜0.01%, refining continuous casting adopt dynamically gently to depress with technology such as induction stirring and prevents component segregation, improve the whole anti-corrosion effect of steel.
The set of dispense of table 2BNS440 is than (component is w%, and surplus is Fe)
The mechanical property of table 3BNS440 coiled sheet sampling
Table 4BNS440 sulfuric acid immersion corrosion test-results (test conditions: 20% sulfuric acid+30 ℃+24h)
Annotate: erosion rate is calculated as follows: V=△ w/ (ST)
Wherein: △ w: weightless (mg); S: surface-area (cm
2); T: soak time (h).
Embodiment two---and four
The mass percent of the various compositions of steel for resisting sulfuric acid dew point corrosion of embodiment two, three, four sees Table 2 NO.2, NO.3, NO.4 hurdle respectively, the mechanical property of product sees Table NO.2, NO.3, the NO.4 hurdle in 3 respectively, and corrosion resistance nature sees Table 4 NO.2, NO.3, NO.4 hurdle respectively.Ca adopts economic addition: 0.0004%-0.0045%, and its unusual effect can be summarized as follows:
1. because by steel grades system proportion design; adopting the Cu-Cr weather resisting steel is the basis; add microalloy elements such as a small amount of Ca, Ti, Sb; make ferrous materials that passivation take place when metallic surface sulfuric acid liquid film corrodes; produce protective membrane in the metallic surface or reduce the dielectric medium corrosion potential; utilize corrosion product to deposit in the metallic surface, anti-corrosion measures such as the generation of Fe+ and diffusion reach the purpose of wanting anticorrosion effect in the prevention acid solution film.
2. can get yield strength Rel 〉=325MPa, tensile strength Rm 〉=440MPa, elongation after fracture A% 〉=22%, the Structural Steel Plate/volume of high comprehensive performance.
3. can get corrosion resistance nature, at 30 ℃ of 20%H
2SO
4In the solution corrosion soak test, be the effect more than 25 times of the corrosion-resistant rate of General Structural Steel.
4. product can be used for making the structural part such as flue, chimney of power industry; The boiler preheating device of chemical metallurgy industry and economizer equipment, air preheater heat exchange element, line of pipes or dehumidification by condensation device; The acidproof heat-proof structural part of tobacco flue-curing equipment etc.
In a word, above embodiment is all under the prerequisite that guarantees acid corrosion-resistant steel mechanical characteristic, significantly improved the acid corrosion-resistant performance, both sulfuric acid dew point corrosion resistant, atmospheric corrosion resistance compared with prior art, has significant substantive distinguishing features and outstanding progress again, can be used for making the fields such as hardware of acidproof corrosion-resistant environment, as structural parts such as the flue of power industry, chimneys; The boiler preheating device of chemical metallurgy industry and economizer equipment, air preheater heat exchange element, line of pipes or dehumidification by condensation device; The acidproof heat-proof structural part of tobacco flue-curing equipment etc.
Claims (4)
1. a steel for resisting sulfuric acid dew point corrosion is characterized in that the mass percent of various compositions is
C:0.05-0.1%, Si:0.1-0.35%, Mn:0.3-0.8%, P:0-0.02%, S:0-0.01%, Cr:0.5-1.0%, Cu:0.2-0.5%, Sb:0.04-0.1%, Ti:0.01-0.06%, Ca:0.0004%-0.001%, surplus is Fe.
2. steel for resisting sulfuric acid dew point corrosion according to claim 1 is characterized in that: the mass percent of described Ca composition is economic addition: 0.0004%-0.0045%.
3. steel for resisting sulfuric acid dew point corrosion according to claim 1 and 2 is characterized in that: based on the Cu-Cr weather resisting steel, interpolation Ca, Ti, Sb, Mn alloying element are smelted and are formed.
4. steel for resisting sulfuric acid dew point corrosion according to claim 3 is characterized in that: under the condition of starvation, Ca is transported in the molten steel.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882315A (en) * | 2012-12-20 | 2014-06-25 | 上海梅山钢铁股份有限公司 | Making method of sulfuric acid dew point corrosion resistant hot continuous rolled steel |
| CN104451457A (en) * | 2014-11-20 | 2015-03-25 | 南京钢铁股份有限公司 | Hot rolled steel strip with resistance to corrosion of hydrochloric acid and sulfuric acid and production method thereof |
| CN104630657A (en) * | 2013-11-15 | 2015-05-20 | 上海梅山钢铁股份有限公司 | Wear-resistant sulfuric-acid-dew-point-corrosion-resistant hot continuous rolled steel and manufacturing method thereof |
| CN104858568A (en) * | 2015-03-31 | 2015-08-26 | 上海焊接器材有限公司 | Gas shielded flux cored welding wire resistant to sulfuric acid dew point corrosion, and preparation method thereof |
| CN105734406A (en) * | 2016-03-29 | 2016-07-06 | 蒋南宁 | High-performance hot-rolled H profile steel resisting atmosphere corrosion and preparation method thereof |
| CN105937010A (en) * | 2016-06-30 | 2016-09-14 | 江阴兴澄特种钢铁有限公司 | Improved 09CrCuSb steel resistant to sulfuric acid dew point corrosion and manufacturing method thereof |
| CN108342654A (en) * | 2018-05-17 | 2018-07-31 | 柳州钢铁股份有限公司 | The manufacturing method of the cold rolling glassed steel of yield strength 230MPa or more |
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2009
- 2009-05-21 CN CN2009100277687A patent/CN101892439A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882315A (en) * | 2012-12-20 | 2014-06-25 | 上海梅山钢铁股份有限公司 | Making method of sulfuric acid dew point corrosion resistant hot continuous rolled steel |
| CN104630657A (en) * | 2013-11-15 | 2015-05-20 | 上海梅山钢铁股份有限公司 | Wear-resistant sulfuric-acid-dew-point-corrosion-resistant hot continuous rolled steel and manufacturing method thereof |
| CN104630657B (en) * | 2013-11-15 | 2017-01-11 | 上海梅山钢铁股份有限公司 | Wear-resistant sulfuric-acid-dew-point-corrosion-resistant hot continuous rolled steel and manufacturing method thereof |
| CN104451457A (en) * | 2014-11-20 | 2015-03-25 | 南京钢铁股份有限公司 | Hot rolled steel strip with resistance to corrosion of hydrochloric acid and sulfuric acid and production method thereof |
| CN104858568A (en) * | 2015-03-31 | 2015-08-26 | 上海焊接器材有限公司 | Gas shielded flux cored welding wire resistant to sulfuric acid dew point corrosion, and preparation method thereof |
| CN105734406A (en) * | 2016-03-29 | 2016-07-06 | 蒋南宁 | High-performance hot-rolled H profile steel resisting atmosphere corrosion and preparation method thereof |
| CN105937010A (en) * | 2016-06-30 | 2016-09-14 | 江阴兴澄特种钢铁有限公司 | Improved 09CrCuSb steel resistant to sulfuric acid dew point corrosion and manufacturing method thereof |
| WO2018001043A1 (en) * | 2016-06-30 | 2018-01-04 | 江阴兴澄特种钢铁有限公司 | Improved 09crcusb steel resistant to sulfuric acid dew point corrosion and preparation method therefor |
| CN105937010B (en) * | 2016-06-30 | 2018-06-19 | 江阴兴澄特种钢铁有限公司 | A kind of modified 09GrCuSb steel for resisting sulfuric acid dew point corrosion and its manufacturing method |
| CN108342654A (en) * | 2018-05-17 | 2018-07-31 | 柳州钢铁股份有限公司 | The manufacturing method of the cold rolling glassed steel of yield strength 230MPa or more |
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