CN101130849A - Anthracene-phenanthrene resid erosion-proof austenitic stainless steel - Google Patents
Anthracene-phenanthrene resid erosion-proof austenitic stainless steel Download PDFInfo
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Abstract
The present invention discloses a kind of austenitic stainless steel capable of resisting refined anthracene phenanthrene residual oil corrosion. It is made up by adopting conventional smelting process, and its component composition includes: (by wt%) carbon content is less than or equal to 0.030% , manganese content is less than or equal to 2%, phosphorus content is less than or equal to 0.030%, sulfur content is less than or equal to 0.030%, silicone content is 1.5%-6.0%, chrome content is 17%-23%, nickel content is 23%-35%, molebdenum content is 6%-12%, copper content is 0.2%-0.8% and the rest is iron.
Description
Technical field
The present invention relates to a kind of alloy, particularly a kind of austenitic stainless steel of anthracene-phenanthrene resid erosion-proof.
Background technology
In the coke-oven plant, some high temperature and corrosive occasion are arranged, Steel Pattern Number is that 304,316 common stainless steel can't meet the demands, and needs to adopt super stainless steel even nickel-base alloy sometimes.The anthracene device of coke-oven plant for example is that the carbolineum with the coal tar distillation gained is raw material, adopt rectifying extract wherein anthracene and the device of carbazole.A board-like solvent recovery tower is arranged in the anthracene device, add the flash oil in the carbolineum when being used for reclaiming rectifying to.Be provided with a luxuriant and rich with fragrance Residual oil recycle pump at the bottom of tower, this phenanthrene Residual oil recycle pump employing Steel Pattern Number is 321 stainless steel manufacturing, because corrosion generally can only be used 3 months, 321 erosion rate surpasses 4 millimeters every year.
Luxuriant and rich with fragrance Residual oil temperature is up to more than 340 ℃, and corrodibility is very strong.The pH value of luxuriant and rich with fragrance Residual oil is about 8, and its main component comprises phenanthrene 30～50%, and anthracene is about 4.1%, and the pyridine salt is about 4%, and naphthalene is about 3%, carbazole about 1.3%.Go back about fluoride ion 6ppm in addition, about chlorion 20ppm, the about 5ppm of fixed ammonia, full sulphur be about 2.7%, and some other not clear thing.Show through hanging test, Steel Pattern Number is that the stainless erosion rate of URB28 surpasses 1.4 millimeters more than every year, Steel Pattern Number is that 2507 stainless erosion rate surpasses 1 millimeter every year, Steel Pattern Number is that 317 stainless erosion rate surpasses 3.73 millimeters every year, also surpasses 1.2 millimeters every year even Steel Pattern Number is the stainless corrosion speed of 904L.Through hanging test, the UNS registration number is that the nickel-base alloy of N06625 goes for this occasion.But this kind alloy price is very expensive, and the smelting of this material needs higher Technology, and domestic how tame mammoth pump manufacturing firm all ability does not smelt this alloy.Therefore choosing suitable material is a problem that presses for solution.
Summary of the invention
Purpose of the present invention is to solve the problems referred to above that prior art exists, and a kind of austenitic stainless steel that can be used for the anthracene-phenanthrene resid erosion-proof that luxuriant and rich with fragrance Residual oil recycle pump is made at the bottom of coke-oven plant's anthracene device solvent recuperation Tata is provided.
The austenitic stainless steel of anthracene-phenanthrene resid erosion-proof of the present invention forms with conventional smelting process refining, and its component and weight percentage are:
Carbon≤0.030%
Manganese≤2%
Phosphorus≤0.030%
Sulphur≤0.030%
Silicon 1.5%～6.0%
Chromium 17%～23%
Nickel 23%～35%
Molybdenum 6%～12%
Copper 0.2%～0.8%
All the other are iron.
In said components, the content of molybdenum is preferably 6%～10%, and perhaps the content of silicon is preferably 1.5%～4%.Perhaps simultaneously the content of molybdenum being preferably is 6%～10%, and it is 2%～4% that the content of silicon is preferably.
Stainless steel of the present invention, its nickel chromium content and Steel Pattern Number are that 6XN is close, but 6XN is nitrogenous, and material of the present invention is nonnitrogenous, and the technical difficulty that this just greatly reduces smelting makes the molding floor of general pump factory to smelt.Material of the present invention is in addition compared with 6XN has also increased silicone content, and this has not only strengthened stainless corrosion resistance nature, has also improved its casting properties, makes this material be more suitable in equipment such as casting pump, valves.Stainless steel of the present invention is the content that 904L compares has increased molybdenum (Mo) and silicon with Steel Pattern Number, has improved corrosion resistance nature, and the occasion that can not use at some 904L might use stainless steel of the present invention to prevent corrosion like this.Because stainless steel of the present invention is compared the content that has increased silicon with 904L, improved casting properties in addition, this just makes stainless steel of the present invention be more suitable in casting pump valve etc.Its analysis of causes is as follows:
1, Mo is to improving the corrosion proof influence of stainless steel
Stainless steel surface has the chromic oxide protective membrane of one deck densification, and this layer passive film plays keying action to stainless solidity to corrosion.In reductant, the passive film of stainless steel surface can suffer corrosion failure, makes stainless steel become activated state by the passivation attitude.Therefore, general stainless steel solidity to corrosion in reductant reduces, and occurs local corrosion easily.Result of study shows, adds an amount of Mo and can improve the corrosion resistance of stainless steel in reductant, improves the anti-spot corrosion of stainless steel, anti-crevice corrosion, the particularly performance of resisting chlorides local corrosion.In this respect, the ability to function of Mo is equivalent to 3 times of Cr.Mo can also improve the mechanical behavior under high temperature of austenitic stainless steel.Mo improve stainless steel in reductant solidity to corrosion, mainly be because molybdate is an anodic inhibitor, the compound action of Mo and Cr can improve stainless passivation and passivation ability (repair ability of passive film) again, can improve the stability of passive film, therefore make stainless steel have better anti-corrosion capability.In reductant, stainless corrosion resistance nature strengthens with the raising of steel grade Mo content.This point is confirmed by a lot of results of study.
The relevant patent of table 1 relatively reaches the solidity to corrosion in the luxuriant and rich with fragrance Residual oil of anthracene
| Patent | Chemical Composition | Typical case's grade of steel | The composition characteristics | Shortcoming | Erosion rate mm/a | |||||||
| C | Mn | Si | Cr | Ni | Mo | N | Cu | |||||
| CN0181 0365.0 | ＜0.8 | 19～ 23 | 30～ 35 | 1～6 | Not corrosion-resistant | 1.2 | ||||||
| US.Pat. 4545826 | ＜1.0 | 18～ 21 | 20～ 30 | 6～12 | 0.18～ 0.25 | 6XN | Nitrogenous | The difficult smelting | 0.1 | |||
| CN0180 9822.3 | 17～ 23 | 19～ 23 | 1～6 | Polira te 778 | Not corrosion-resistant | 1.0 | ||||||
| CN2006 1002330 3.0 | ≤ 0.03 | ≤ 1.5 | ＜1.5 | 19～ 23 | 24～ 27 | 5.5～ 6.5 | ≤0.2 | ≤1.5 | Nitrogenous | Difficult the smelting | ||
| The present invention | ≤ 0.03 | 1.5～ 6.0 | 17～ 23 | 23～ 35 | 6～12 | 0.2～ 0.8 | Nonnitrogenous, siliceous, molybdenum | Be easy to smelt | ＜0.1 | |||
Annotate: erosion rate refers to the data of material in the luxuriant and rich with fragrance Residual oil of anthracene device.
High-performance stainless steel also claims super stainless steel, and these stainless steels belong to high-purity, high Cr, high Mo nitrogen-contained stainless steel.Table 1 is the super austenitic stainless steel of having produced both at home and abroad at present.Raising Cr, Mo content are the important channels of improving stainless steel solidity to corrosion and mechanical property.The high-performance austenitic stainless steel generally contains 4%～6% Mo, and the molybdenum content of 654SMo steel reaches 7%.But contain the molybdenum amount at present and all contain nitrogen above in 5% the super stainless steel.These steel all have excellent solidity to corrosion in Oxidant and reductant, but seawater corrosion resistance, anti-various chloride media uniform corrosion and local corrosion.Good solidity to corrosion is arranged in sulfuric acid and phosphoric acid, can reach the level of Alloy C-276 nickel-base alloy as 654SMo steel resisting chlorides corrosion and the various local corrosion performances in seawater.High-performance stainless steel is mainly used in manufacturing: papermaking bleaching equipment, condenser tubes, STP, high temperature seawater heat exchanger, reverse method desalination production unit, garbage incinerating system, environmental protection and thermal power station's waste gas wet desulphurization equipment (FGD), phosphoric acid strainer and blender parts, sulfur waste acid thickening equipment and pollution-free pharmaceutical equipment etc.
Just because of molybdenum can be bigger the corrosion resistance nature of raising stainless steel in reductant, therefore stainless steel of the present invention is compared with 904 serial super stainless steels, increase content to 6～12% of molybdenum, improved the corrosion resistance nature of stainless steel of the present invention in reductant significantly.Lacing film experiment has repeatedly also confirmed the corrosion resistance nature of molybdenum, and Steel Pattern Number is that 6XN and 625 alloys all contain molybdenum more than 6%, can both satisfy the corrosion-resistant requirement of the luxuriant and rich with fragrance Residual oil of anthracene.
2, nitrogen is to improving the corrosion proof influence of stainless steel
The effect more complicated of nitrogen in stainless steel remains deep discussion.So far result of study can be summarized as following some: 1., N mainly is the solution strengthening by N, the dispersion-strengthened of nitride and the performance that three kinds of approach of grain refining improve steel in stainless steel; 2., N can improve the intensity of austenitic stainless steel and duplex stainless steel, and don't reduces toughness, N can also improve stainless creep-resistant property; 3., in some media environment, N can improve stainless corrosion resistance, comprises anti-stress corrosion performance, anti-pitting attack performance and anti-cavitation corrosion polishing machine; 4., with the alloying of N for Ni, the development that casting is contained N ultra hypoeutectoid, diphasic stainless steel and nickelles stainless steel has important use to be worth; 5., refining techniquess such as AOD, VOD provide advanced manufacturing process for producing pure nitrogen-contained stainless steel, and can reduce stainless cost.
This shows that only in some media environment, N just can improve stainless corrosion resistance.In many occasions, nitrogen is not remarkable to stainless corrosion resistance influence.But the production technique of nitrogen-contained stainless steel is but very complicated, the cost of equipment costliness.Especially in casting on a small scale during electromechanical equipment, that is that all right is ripe for the foundry engieering of nitrogen-contained stainless steel.The nitrogen-contained stainless steel steel ingot of atmosphere melting, be difficult to form the high-quality steel owing to forming a large amount of gas hole defects, so high nitrogen stainless steel must adopt melting and foundry engieering under high-pressure atmosphere, and nitrogen is in the mensuration of stainless steel melt solubleness, though direct method and indirect method are arranged, but empirical very strong, also be difficult to accurately control.Therefore the smelting technology of nitrogen-contained stainless steel has only only a few large-size stainless steel enterprise to grasp, then very difficult grasp of general big-and-middle-sized pump factory.And pump factory can not buy steel billet and carry out melting, because nitrogen can escape in the process of melting.Simultaneously, the large-size stainless steel smeltery lacks the casting proprietary technology of pump, and the manufacturing issue of the pump of nitrogen-contained stainless steel just becomes a very complicated problems like this.
Lacing film repeatedly experiment showed, some unazotized stainless steels, also can satisfy the corrosion-resistant requirement of the luxuriant and rich with fragrance Residual oil of anthracene as C4 (00Cr14Ni14Si4) and 17175 (00Cr17Ni17Si5).Stainless steel of the present invention is compared nonnitrogenous with 6XN, the corrosion resistance nature in the luxuriant and rich with fragrance Residual oil medium of anthracene does not descend, but has simplified stainless smelting process greatly, makes pump factory Foundry Production pump become many easily.
3, silicon is to improving the influence of stainless steel solidity to corrosion and casting properties
Silicon is one of important non-corrosive metal element, has good antioxidant property, when containing silicon in the stainless steel, can generate SiO on stainless surface
2Oxide film, this film has higher resistivity and chemical stability, and in Oxidant, the austenitic stainless steel corrosion resistance nature of high silicon increases significantly.Anodic reaction has been quickened in the interpolation of Si, has weakened cathodic reaction, farthest contains silicon the corrosion resisting property of material is highly profitable.The adding of silicon is significantly improved the chemical property of austenitic stainless steel.The adding of silicon accelerated stainless steel in medium by the transformation of active state to passive state.The silicon-containing compound that silicon and elemental iron, chromium, nickel form has played the effect that promotes passivation to stainless anti-corrosion behavior, and silicon and chromium, nickel element have composite passivated effect in stainless steel.
The adding of silicon has also improved the flowability of stainless steel liquation except making stainless corrosion resistance nature raising, improved stainless casting properties.
Lacing film experiment showed, the multiple silicon stainless steel that contains, and as C4 (00Cr14Ni14Si4), 17175 (00Cr17Ni17Si5), can be fit to the corrosion-resistant requirement of the luxuriant and rich with fragrance Residual oil of anthracene.But these two kinds of steel castabilitys are all bad.Stainless steel of the present invention is compared with 6XN with 904, has increased the content of silicon, and this just makes this stainless corrosion resistance nature might surpass 904 and 6XN.
The anti-luxuriant and rich with fragrance Residual oil corrosive austenitic stainless steel of the present invention makes it compared with prior art owing to adopted above technical scheme, has following advantage and characteristics:
1, cheap, the price of the anti-luxuriant and rich with fragrance Residual oil corrosive austenitic stainless steel of the present invention is 1/10th of alloy 625 materials, also than 6XN cheap half;
2, smelting technology is simple, and general big-and-middle-sized pump factory can both smelt, and alloy 625 and 6XN be because nitrogenous, and smelting technology is difficult to, and general big-and-middle-sized pump factory can not smelt;
3, excellent anti-corrosion performance, corrosion resistance nature and the alloy 625 of the anti-luxuriant and rich with fragrance Residual oil corrosive austenitic stainless steel of the present invention in the luxuriant and rich with fragrance Residual oil of anthracene is suitable with 6XN, is better than 317, stainless steels such as 904L;
4, be easy to casting, though C4 (00Cr14Ni14Si4) and 17175 (00Cr17Ni17Si5) can be fit to the corrosion-resistant requirement of the luxuriant and rich with fragrance Residual oil of anthracene, these two kinds of steel castabilitys are all bad, are difficult to make pump.
Embodiment
The austenitic stainless steel of anthracene-phenanthrene resid erosion-proof of the present invention can adopt methods such as electric arc furnace, induction furnace, VOD or vacuum induction furnace to smelt.The step that wherein adopts VOD to smelt is as follows:
1, batching and charging
Add stainless steel steel scrap, carbon element steel scrap, nickel, molybdenum card, starting material such as ferrochrome according to chemical ingredients.
2, fusing
Use furnace melting.
3, refining just in electric furnace
Be decarburization, silicon and sulphur, make molten steel carbon content and temperature reach the concise requirement of VOD;
After the molten bath is molten clear, oxygen decarburization immediately.In high Cr steel liquid, adopt the oxygen steelmaking method to reach more satisfactoryly and take off the purpose that C protects Cr.
4, molten steel reduction
After taking off the C end, in molten steel, add extra low carbon ferrochromium or Metal Cr, utilize high-temperature molten steel to melt, make the molten steel cooling simultaneously.The liquid steel temperature of reduction period should drop to below 1700 ℃, also will add the returns cooling of a part with steel grade in case of necessity.
A considerable amount of Cr are oxidized to be entered in the slag owing to having oxidation period, needs to add reductive agent in slag it is reduced.Reductive agent is to use carbon content below 0.10%, and the ferrosilicon of silicon content 75% or ferrosilicon powder are main.
For improving the yield of Cr, slag basicity should reach more than 1.5%, should add the lime with ferrosilicon equivalent in the molten bath for this reason.
5, refining
Molten steel is continued decarburization and reduction refining with the VOD method, produce satisfactory stainless steel.
The purified main task is the further adjustment of further deoxidation, desulfurization and temperature and composition.Ti, Nb and Re are the active metals, and portion should add the refining period before tapping.Optimal method is that wire feed method carries out alloying, and its rate of recovery can reach 90%.
6, tapping
Tapping temperature has material impact to the solidified structure and the casting quality of steel billet or steel ingot.
Technologies such as the available common sand mold in tapping back, resin bonded sand mould and precision casting are cast.
Carry out 1100～1200 ℃ of solution treatment after the casting, soaking time is more than 2 hours.
Each components contents in the stainless steel can on-line Control and adjustment in smelting process, in a kind of product that contriver's refining obtains beyond the iron each components contents be: carbon 0.023%, manganese 2.0%, phosphorus 0.030%, sulphur 0.03%, silicon 2.0%, chromium 20%, nickel 25%, molybdenum 6.7% and copper 0.6%.Made as the luxuriant and rich with fragrance Residual oil recycle pump at the bottom of coke-oven plant's anthracene device solvent recuperation Tata of this product stainless steel, through producing checking, this stainless erosion rate can satisfy processing requirement less than 0.1 millimeter/year, has solved the etching problem of the luxuriant and rich with fragrance Residual oil of anthracene.
The difference of stainless steel of the present invention and prior art and improvement further specify as follows:
Chinese patent publication number CN01810365.0 discloses a kind of austenitic stainless steel, and it comprises 19～23% chromium, 30～35% nickel, 1～6% molybdenum and less than 0.8% silicon.The molybdenum that stainless steel of the present invention adds surpasses 6%, strengthened high-temperature corrosion resistance, and the disclosed stainless steel molybdenum of CN01810365.0 content is less than 6%.The present invention has increased the content of molybdenum, has improved stainless corrosion resistance nature.Stainless steel of the present invention, the content of silicon has improved casting properties more than 1.5%, and the disclosed stainless steel silicone content of CN01810365.0 is lower than 0.8%.The present invention has increased silicone content, has improved stainless casting properties, helps making pump.
The disclosed stainless steel of U.S. Pat .Pat.4545826 comprises 18～21% chromium, 20～30% nickel, 6～12% molybdenum and 0.18～0.25% nitrogen.Stainless steel of the present invention is nonnitrogenous, and US.Pat.4545826 is then nitrogenous.6XN is a proprietary concentrate of this patent of US.Pat.4545826, and its composition is: carbon≤0.030%, manganese≤2.00%, phosphorus≤0.040%, sulphur≤0.030%, silicon≤1.0%, chromium 20～22%, nickel 23～25%, molybdenum 6～7% and copper 0.1～0.75%.Stainless steel of the present invention is nonnitrogenous, and the disclosed stainless steel of US.Pat.4545826 nitrogenous 0.18～0.25%; The content of stainless steel silicon of the present invention is greater than 1.5%, and the disclosed stainless steel of US.Pat.4545826 does not have the requirement of silicone content.Stainless steel of the present invention is nonnitrogenous and siliceous, is easy to produce, and is easy to metallurgy and foundry, and the molding floor of general pump all can make.And the disclosed stainless metallurgy and foundry technology of US.Pat.4545826 has only the large-size stainless steel smeltery to grasp usually.
Chinese patent publication number CN01809822.3 discloses a kind of austenitic stainless steel, comprises 17～23% chromium, 19～23% nickel, 1～6% molybdenum.Stainless steel molybdenum content of the present invention surpasses 6%, and nickel content surpasses 23%, and cupric 0.2～0.8%, compares with CN01809822.3, has increased the content of molybdenum, nickel and copper, and this has just strengthened high-temperature corrosion resistance.
The present invention compares with Chinese patent application CN200610023303.0, and is nonnitrogenous, and improved the content of silicon and molybdenum.The disclosed stainless steel nitrogen content of CN200610023303.0 is less than 0.15%, and silicone content is less than 1.5%, and molybdenum content is 5.5～6.5%.And stainless steel of the present invention is nonnitrogenous, and silicone content is between 1.5～6%, and molybdenum content is between 6～7.Stainless steel of the present invention has reduced the melting difficulty, has strengthened high-temperature corrosion resistance, has improved casting properties, helps making pump.
Claims (4)
1. the austenitic stainless steel of an anthracene-phenanthrene resid erosion-proof forms with conventional smelting process refining, and its component and weight percentage are:
Carbon≤0.030%
Manganese≤2%
Phosphorus≤0.030%
Sulphur≤0.030%
Silicon 1.5%～6.0%
Chromium 17%～23%
Nickel 23%～35%
Molybdenum 6%～12%
Copper 0.2%～0.8%
All the other are iron.
2. stainless steel as claimed in claim 1 is characterized in that: wherein the content of molybdenum is 7%～10%.
3. stainless steel as claimed in claim 1 is characterized in that: wherein the content of silicon is 1.5%～4%.
4. stainless steel as claimed in claim 1 is characterized in that: wherein the content of molybdenum is 7%～10%, and the content of silicon is 1.5%～4%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383070A (en) * | 2011-10-25 | 2012-03-21 | 安泰科技股份有限公司 | Additive for B-Si containing iron-based amorphous alloy and nanocrystalline alloy |
| CN103667853A (en) * | 2013-12-04 | 2014-03-26 | 蚌埠华泰特种钢有限公司 | Two-step method for smelting titanium-containing austenitic stainless steel |
| CN112375957A (en) * | 2020-11-12 | 2021-02-19 | 江苏金研新材料科技有限公司 | Nickel-iron-based corrosion-resistant alloy and preparation method thereof |
| CN113088796A (en) * | 2021-03-04 | 2021-07-09 | 南昌大学 | Preparation method of Ti modified 904L alloy applied to high-temperature oxidizing chlorine-containing atmosphere |
-
2006
- 2006-08-24 CN CNA2006100303673A patent/CN101130849A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383070A (en) * | 2011-10-25 | 2012-03-21 | 安泰科技股份有限公司 | Additive for B-Si containing iron-based amorphous alloy and nanocrystalline alloy |
| CN103667853A (en) * | 2013-12-04 | 2014-03-26 | 蚌埠华泰特种钢有限公司 | Two-step method for smelting titanium-containing austenitic stainless steel |
| CN112375957A (en) * | 2020-11-12 | 2021-02-19 | 江苏金研新材料科技有限公司 | Nickel-iron-based corrosion-resistant alloy and preparation method thereof |
| CN112375957B (en) * | 2020-11-12 | 2021-10-22 | 江苏金研新材料科技有限公司 | Nickel-iron-based corrosion-resistant alloy and preparation method thereof |
| CN113088796A (en) * | 2021-03-04 | 2021-07-09 | 南昌大学 | Preparation method of Ti modified 904L alloy applied to high-temperature oxidizing chlorine-containing atmosphere |
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