CN101892438B - Rare earth low alloy steel with high-temperature sulfuric acid dew point corrosion resistance - Google Patents
Rare earth low alloy steel with high-temperature sulfuric acid dew point corrosion resistance Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000007797 corrosion Effects 0.000 title claims abstract description 64
- 238000005260 corrosion Methods 0.000 title claims abstract description 64
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 23
- 229910000851 Alloy steel Inorganic materials 0.000 title claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000000295 fuel oil Substances 0.000 abstract description 4
- 239000010742 number 1 fuel oil Substances 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003546 flue gas Substances 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 26
- 239000010959 steel Substances 0.000 description 26
- 239000010949 copper Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
The invention discloses rare earth low alloy steel with high-temperature sulfuric acid dew point corrosion resistance, which comprises the following chemical components in percentage by weight: less than or equal to 0.10 percent of C, less than or equal to 0.1 percent of Si, 0.5 to 2.0 percent of Mn, less than or equal to 0.20 percent of P, less than or equal to 0.050 percent of S, 0.5 to 1.0 percent of Cu, 0.7 to 2.0 percent of Cr, less than or equal to 0.010 percent of Ti, less than or equal to 0.50 percent of Ni, 0.01 to 0.5 percent of Mo, less than or equal to 0.60 percent of RE( La, Ce ),and the balance of Fe, wherein the ratio of Cu to S is 30 to 40. The rare earth low alloy steel has the high high-temperature sulfuric acid dew point corrosion resistance, and is widely applied to flue gas treatment systems taking coal or heavy oil as a main fuel.
Description
Technical field
The invention belongs to the ferrous metallurgy field, relate to a kind of corrosion-resistant steel, specifically a kind of rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance.
Background technology
At industrial circles such as electric power, metallurgy, petrochemical industry; With coal or heavy oil is the smoke processing system of main fuel; Air preheater, economizer, flue, chimney and desulfurizer etc. like the boiler low-temperature position; It is higher generally can to run in the fuel sulphur content, under dew-point temperature, forms sulfuric acid and causes the equipment corrosion problem, and this is referred to as the phenomenon of " sulfuric acid dew point corrosion ".Different with common atomospheric corrosion, this corrosion not only makes plain carbon stool corroded, and stainless steel is also corroded, and is therefore very harmful.
The mid-80, the development and production of Co., Ltd. of Japanese Nippon Steel the new S-TEN1 of sulfuric acid corrosion resistant steel, S-TEN2,95 years SUMITOMO CHEMICAL companies also development and production sulfuric acid corrosion resistant steel CRIA, and use to a lot of business enterprise expands of China.Prove that through life-time service this type steel grade of Japan more adapts to its national practical situation, can not reach the ideal effect in China.Its major cause has: China's major part is the electricity power enterprise of main fuel with the coal, and the main coal type that adopts is a meager lean coal, and the high energy of its sulphur content reaches 3%, has surpassed the 2.5% high sulfur content standard of stipulating among the standard GB 50051-2002.The power plant burning of Japan is lower with the coal sulphur content, and the difference of environment for use makes the weak effect of its generation apart from very big.
Steel in the past, for using sulphur content can not bring into play sufficient solidity to corrosion above 2% the equipment that contains high-sulfur fuel, when sulphur content increased, the sulfuric acid concentration in the exhaust increased, and followed temperature to reduce, and the vitriolic condensation number increases.As corrosive environment, harsher than the occasion that contains low-sulfur fuel.Therefore,, sulphur content can bring into play the steel clock of excellent corrosion resistance nature in being lower than 2% comparatively gentle environment, the excellent solidity to corrosion of performance not necessarily in the environment of high-sulfur fuel.Also do not have a kind of high-temperature sulfuric acid dew point corrosion resistance steel at present, promptly can in the high-sulfur fuel environment, have excellent corrosion proof steel grade.And in the environment of high-sulfur fuel, discharging the sulphuric acid dew point of gas about 110-160 ℃ condenses, at the high-concentration sulfuric acid that adheres on the steel surface about sulfuric acid concentration 70-90%.
Summary of the invention
In order to overcome the problem that prior art exists, the purpose of this invention is to provide a kind of rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance.This low alloy steel has excellent high-temperature sulfuric acid dew point corrosion resistance performance.
The objective of the invention is to realize through following technical scheme:
A kind of rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance is characterized in that: the weight percent that the rare earth low alloy steel of this high-temperature sulfuric acid dew point corrosion resistance contains chemical ingredients is: C≤0.10%, Si≤0.1%, Mn 0.5%-2.0%; P≤0.020%, S≤0.050%, Cu 0.5%-1.0%; Cr 0.7%-2.0%, Ti≤0.010%, Ni≤0.50%; Mo 0.01-0.5%, RE≤0.60%, all the other are Fe.Wherein Cu/S is 30-40.
Among the present invention, said REE (RE) is the mixture of La or Ce or La and Ce, and its content is La≤0.60% or Ce≤0.60% or (La+Ce)≤0.60% by weight percentage.RE (La, Ce)/S is 10-30.
The chemical component weight per-cent of this high-temperature sulfuric acid dew point corrosion resistance low alloy steel according to the invention is: C:0.098%, Si:0.08, Mn:1.69%, P:0.020%; S:0.020%, Cu:0.80%, Cr:1.35%; Ti:0.010%, Ni:0.22%, Mo 0.15%; RE (La, Ce) 0.50%, all the other are Fe.
The qualification reason of composition of steel is set forth as follows among the present invention:
In oxidizing acid, when carbon content＜0.4%, increase with carbon content, the solidity to corrosion of steel improves, but when coexisting with Cu, C makes the solidity to corrosion of steel that decline is arranged slightly again.The solidity to corrosion of low-carbon (LC) Copper Bearing Steel is the most excellent.Because carbon content is low more, then the unrelieved stress of steel plate is low more, so carbon content is preferably accessible low-levelly, and preferred carbon content is≤0.1%
Cu has vital role to the solidity to corrosion that improves steel, and S, P then is the harmful element in the steel, content is low more good more.But concerning sulfuric acid dew point corrosion resistant, a certain amount of S exists, and can impel the surface of steel to form Cu
2S passive film, thereby the electrochemical reaction of inhibition anodic reaction and negative electrode.If contain the S quantity not sufficient, Cu
2The S surface film just can not form, and Cu just is deposited in the surface, has increased annode area, on the contrary accelerated corrosion.So the content of Cu and S should meet certain ratio, for high-temperature sulfuric acid dew point corrosion resistance, being preferably Cu/S is 30-40.
Mn is to strengthening effective elements, under the situation that the intensity that the low carbonization that is necessary to fill up as the present invention causes reduces, can containing in right amount.But when its content surpasses 3.0%, not only can make the corrosion resistance nature variation, the solidity to corrosion that solidity to corrosion deterioration even counteracting are brought by extremely lowization of C is improved effect, and therefore preferred manganese content is 0.5%-2.0%.
Cr is favourable to the solidity to corrosion that improves steel, and preferred chromium content is 0.7%-2.0%.
Ti except crystal grain thinning, raising intensity, can also improve the welding property of steel in steel, but unfavorable to sulfuric acid corrosion resistant.Especially work as its content and surpass 0.01%, can make the corrosion resistance nature variation, preferred titanium content is≤0.010%.
Ni can use for the hot workability variation that prevents copper, still, when its content surpasses 0.5%, can make the corrosion resistance nature variation, and preferred nickel content is≤0.50%.
Mo exists the occasion of hydrogenchloride to help to improve corrosion proof element in exhaust, but contains unfavorablely to the vitriolic solidity to corrosion sometimes in a large number, and therefore preferred molybdenum content is 0.01-0.50%.
Rare earth (RE) has great affinity interaction to low melting point metal in the steel and nonmetal composition, thereby improves the bonding force of steel surface corrosion product film and matrix, delays corrosion products film from the time that matrix comes off, and reduces the erosion rate of steel.Select for use rare-earth elements La commonly used and Ce as adding element, and preferably its content is≤0.6%, and RE (La, Ce)/S is controlled to be 10-30.
The present invention recently makes steel reach best high-temperature sulfuric acid dew point corrosion resistance performance through the weight percent of various compositions in the control steel.The material that to be made by invention is at 70%H
2SO
4-110 ℃ and 90%H
2SO
4Under-160 ℃ of conditions, carry out immersion test according to GB GB10124-88.Compare with other corrosionproof steel against sulfuric acid at dew point, show that high-temperature sulfuric acid dew point corrosion resistance performance of the present invention obviously is superior to other corrosionproof steel against sulfuric acid at dew point.The present invention has excellent high-temperature sulfuric acid dew point corrosion resistance performance, and it is adaptable across being in the smoke processing system of main fuel with coal or heavy oil.
Description of drawings
The corrosion weight loss speed synoptic diagram that Fig. 1 soaks in sulphuric acid soln for the present invention.
The corrosion weight loss speed synoptic diagram that Fig. 2 soaks in sulphuric acid soln for comparative example 1.
The corrosion weight loss speed synoptic diagram that Fig. 3 soaks in sulphuric acid soln for comparative example 2.
Embodiment
Embodiment
A kind of rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance of the present invention, the chemical ingredients of the rare earth low alloy steel of this high-temperature sulfuric acid dew point corrosion resistance is seen table 1, selects for use rare-earth elements La and Ce as adding element, and wherein La is 0.3%, and Ce is 0.2%.
Table 1: the chemical ingredients of present embodiment (quality %)
| Composition | C％ | Si％ | Mn％ | P％ | S％ | Cu％ | Cr％ | Ti％ | Ni％ | Mo％ | RE％ |
| Embodiment | 0.098 | 0.08 | 1.69 | 0.020 | 0.020 | 0.80 | 1.35 | 0.010 | 0.22 | 0.1 | 0.5 |
Adopt the described alloying constituent of present embodiment to make experiment material, experiment lacing film line is cut into the rectangle lacing film of 50mm * 30mm * 4.5mm, and the hole of on sample, boring φ 3mm, is convenient to suspension.At 70%H
2SO
4-110 ℃ and 90%H
2SO
4Under-160 ℃ of conditions, carry out the 24h+48h+72h+96h immersion test according to GB GB10124-88.
Experimental result is as shown in Figure 1.From Fig. 1, can find at 70%H
2SO
4-110 ℃ and 90%H
2SO
4Under-160 ℃ of conditions, corrosion weight loss speed of the present invention is 0.11-0.15mm/a, and erosion rate is lower; And along with the prolongation of soak time, erosion rate reduces gradually, and tends towards stability; Explanation has formed fine and close corrosion products film in the metallic surface, inhibited to further corrosion.The present invention has excellent high-temperature sulfuric acid dew point corrosion resistance performance.
Comparative example 1
The alloying constituent of comparative example 1 material is seen table 2.
Table 2: the chemical ingredients (quality %) of comparative example 1 experiment material
| Sample | C％ | Si％ | Mn％ | P％ | S％ | Cu％ | Al％ | Sb％ | Mo％ | V％ |
| Comparative example 2 | 0.027 | 0.09 | 2.01 | 0.008 | 0.011 | 0.50 | 0.018 | 0.11 | 0.5 | 0.03 |
Adopt comparative example 1 described steel alloy to make experiment material, experiment lacing film line is cut into the rectangle lacing film of 50mm * 30mm * 4.5mm, and the hole of on sample, boring φ 3mm, is convenient to suspension.At 10%H
2SO
4-30 ℃, 30%H
2SO
4-50 ℃ and 50%H
2SO
4Under-70 ℃ of conditions, carry out the 24h+48h+72h+96h immersion test according to GB GB10124-88.
Experimental result is as shown in Figure 2.From Fig. 2, can find at 70%H
2SO
4-110 ℃ and 90%H
2SO
4Under-160 ℃ of conditions, the corrosion weight loss speed of comparative example 1 is 0.10-0.18mm/a, and relative the present invention is higher for erosion rate, and along with the prolongation of soak time, erosion rate increases gradually, explains and fails to form the corrosion products film with protectiveness in the metallic surface.
This is because the Cu/S in the comparative example 1 is 46, has surpassed copper sulphur ratio of the present invention, causes to contain S quantity not sufficient, Cu
2The S surface film just can not form, and Cu just is deposited in the surface, has increased annode area, on the contrary accelerated corrosion.Thereby make its high-temperature sulfuric acid dew point corrosion resistance poor-performing.
Comparative example 2
The alloying constituent of comparative example 2 materials is seen table 3.
Table 3: the chemical ingredients (quality %) of comparative example 2 experiment materials
| Sample | C％ | Si％ | Mn％ | P％ | S％ | Cu％ | A1％ | B％ |
| Comparative example 1 | 0.029 | 0.077 | 0.21 | 0.009 | 0.006 | 0.31 | 0.025 | 0.0010 |
Adopt comparative example 2 described steel alloys to make experiment material, experiment lacing film line is cut into the rectangle lacing film of 50mm * 30mm * 4.5mm, and the hole of on sample, boring φ 3mm, is convenient to suspension.At 10%H
2SO
4-30 ℃, 30%H
2SO
4-50 ℃ and 50%H
2SO
4Under-70 ℃ of conditions, carry out the 24h+48h+72h+96h immersion test according to GB GB10124-88.
Experimental result is as shown in Figure 3.From Fig. 3, can find at 70%H
2SO
4-110 ℃ and 90%H
2SO
4Under-160 ℃ of conditions; The corrosion weight loss speed of comparative example 2 is 0.10-0.20mm/a, and relative the present invention of erosion rate and comparative example 1 further increase, and along with the prolongation of soak time; Erosion rate increases gradually, explains and fails to form the corrosion products film with protectiveness in the metallic surface.
This is because the Cu/S in the comparative example 2 is 51, has surpassed copper sulphur ratio of the present invention, causes to contain S quantity not sufficient, Cu
2The S surface film just can not form, and Cu just is deposited in the surface, has increased annode area, on the contrary accelerated corrosion.Thereby make its high-temperature sulfuric acid dew point corrosion resistance poor-performing.
High-temperature sulfuric acid dew point corrosion resistance performance of the present invention obviously is superior to other corrosionproof steel against sulfuric acid at dew point, has excellent high-temperature sulfuric acid dew point corrosion resistance performance, and it is adaptable across being in the smoke processing system of main fuel with coal or heavy oil.
Claims (3)
1. the rare earth low alloy steel of a high-temperature sulfuric acid dew point corrosion resistance, it is characterized in that: the weight percent that the rare earth low alloy steel of this high-temperature sulfuric acid dew point corrosion resistance contains chemical ingredients is: C≤0.10%, Si≤0.1%, Mn 0.5%-2.0%; P≤0.020%, S≤0.050%, Cu 0.5%-1.0%; Cr 0.7%-2.0%, Ti≤0.010%, Ni≤0.50%; Mo 0.01-0.5%, RE≤0.60%, all the other are Fe; It is 30-40 that the weight percent of said Cu and S satisfies Cu/S; It is 10-30 that the weight percent of said RE and S satisfies RE/S.
2. the rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance according to claim 1; It is characterized in that: said RE is the mixture of La or Ce or La and Ce, and its content is La≤0.60% or Ce≤0.60% or (La+Ce)≤0.60% by weight percentage.
3. the rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance according to claim 1, it is characterized in that: the chemical component weight per-cent of said high-temperature sulfuric acid dew point corrosion resistance rare earth low alloy steel is: C:0.098%, Si:0.08, Mn:1.69%; P:0.020%, S:0.020%, Cu:0.80%; Cr:1.35%, Ti:0.010%, Ni:0.22%; Mo 0.15%, and RE 0.50%, and all the other are Fe.
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| CN111206178A (en) * | 2020-02-24 | 2020-05-29 | 包头钢铁（集团）有限责任公司 | Rare earth steel for resisting sulfuric acid dew point corrosion and preparation method thereof |
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| JP2564425B2 (en) * | 1990-12-20 | 1996-12-18 | 新日本製鐵株式会社 | Manufacturing method of high toughness 40kg class steel pipe with excellent SSC resistance |
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| JP昭57-120615A 1982.07.27 |
| JP特开平4-221018A 1992.08.11 |
| 徐军等.耐硫酸露点腐蚀用NS1 钢的开发和应用.《华东电力》.1999,(第6期),48-51. * |
| 钱余海等.低合金耐硫酸露点腐蚀钢的性能和应用.《特殊钢》.2005,第26卷(第5期),30-34. * |
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