CN101368249B - Steel for boiler and method of producing the same - Google Patents
Steel for boiler and method of producing the same Download PDFInfo
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Abstract
The invention discloses steel used for a boiler and a manufacture method thereof. The invention is mainly characterized by including the chemical elements with the following weight percentage: 0.04 to 0.10 percent of C, equal to or less than 0.50 percent of Si, equal to or less than 2.00 percent of Mn, 8.00 to 12.00 percent of Ni, 17.00 to 19.00 percent of Cr, 0.8 to 1.00 percent of Nb, equal to less than 0.25 percent of Cu, equal to or less than 0.015 percent of S, equal to or less than 0.040 percent of P, 0.005 to 0.040 percent of B, 0.10 to 0.20 percent of N, 0.005 to 0.100 percent of N and the rest is Fe as well as unavoidable impurities. The process flow of the invention is as follows: primary melting by an electric arc furnace, AOD refining, die casting, primary rolling, roughing or continuous casting, rolling a tube blank in a hot way and manufacturing a tube. The steel used for a boiler and a manufacture method thereof can solve the problems that steel tube used by the prior boiler is lower in intensity and is easy to generate a fatigue crack, and the like. Besides, the steel used for a boiler and a manufacture method thereof can further improve the comprehensive mechanical performances and the service life of the steel tube used for a boiler.
Description
Technical field
The present invention relates to a kind of composition design and manufacture method thereof of austenite heat-resistance stainless steel, refer in particular to supercritical thermal power generating set boiler high strength, high temperature resistant, high compressed steel.
Background technology
Along with national power demand increases severely, development large vol, overcritical, ultra supercritical parameter fired power generating unit are the our times trends.Parameter (pressure and temperature) is high more, and the energy that it can be changed is also many more, and the efficient of unit is just high more.Overcritical, ultra supercritical generating set boiler also upgrades in continuous development with metallic substance, requires boiler steel not only to have enough creep rupture strengths when long, but also higher oxidation-resistance will be arranged.
At present, China's generated energy is taked the thermal power generation mode more than 80%.The general supercritical generating unit that adopts, the main grade of steel of employing is 1Cr19Ni11Nb, its chemical ingredients is: carbon: 0.04～0.10%, silicon :≤0.75%, manganese :≤2.00%, nickel: 9.00～13.00%, chromium: 17.00～20.00%, niobium: 8*C～1.00%, copper :≤0.25%, sulphur :≤0.020%, phosphorus :≤0.035%, V≤0.10%, B≤0.010%, surplus is Fe and minor impurity.
Above-mentioned 1Cr19Ni11Nb supercritical generating unit is electric arc furnace steel, AOD refining, static ingot, 800 milling train breaking down coggings, 550 open-train mills or bar continuous rolling unit hot-rolled finished product with stainless manufacturing process, pays pipe mill or user and makes steel pipe.1230 ℃～1270 ℃ of 1Cr19Ni11Nb breaking down cogging temperatures, 1140 ℃～1180 ℃ of hot rolling Heating temperatures, the tensile strength 〉=520MPa after the sample solution treatment, yield strength 〉=205MPa, elongation 〉=40%, relative reduction in area 〉=50%.But the subject matter that this material exists is: high temperature endurance performance and high-temperature oxidation resistance are poor, cause the plugging phenomenon in the use, have reduced the service efficiency of unit, and cost of electricity-generating is improved.
By retrieving domestic and international patent database, retrieve 4 of the information relevant altogether: 1. application number CN00803866.X heat resistant austenitic stainless steel with steel of the present invention; 2. the austenitic stainless steel of application number CN03110437.1 hot strength and corrosion resistance excellent; 3. application number CN97192456.2 new austenitic stainless steel alloy; 4. application number CN98123173.X austenitic stainless steel with good oxidation resistance.
Chemical ingredients (wt%) compares:
| Patent application | C | Si | Mn | Ni | Cr | Mo | w | Cu | Nb | N | B | Rare earth |
| CN0080 3866.X | 0.04～0.10 | ≤ 0.40 | ≤ 0.60 | 22.50～32.00 | 20.00～27.00 | ≤ 0.50 | 0.40～4.00 | 0.20～0.60 | 0.10～0.30 | 0.002～0.008 | － | |
| CN03110 437.1 | 0.03～0.12 | 0.10～1.00 | 0.10～2.00 | 35.00～50.00 | 20.00～28.00 | ≤ 0.50 | 4.00 10.00 | 0.01～1.00 | ≤ 0.02 | 0.0005～0.0100 | － |
| Patent application | C | Si | Mn | Ni | Cr | Mo | w | Cu | Nb | N | B | Rare earth |
| CN971924 56.2 | ≤ 0.12 | ≤ 0.10 | ≤ 2.00 | 8.00～ 14.00 | 16.00～ 22.00 | ≤ 1.00 | － | － | 8*C～ 1.00 | ≤ 0.05 | － | ≤ 0.03 but 0.10 |
| CN98123 173.X | ≤ 0.12 | ≤ 1.00 | ≤ 2.00 | 8.00～ 14.00 | 16.00～ 22.00 | ≤ 1.00 | － | － | 8℃～ 1.00 | ≤ 0.05 | － | 〉=0.02 also≤0.11 |
CN00803866.X, CN03110437.1 invention steel contain higher chromium, nickel content and W elements, at high temperature have high intensity, good steam oxidation patience, good boiler face corrosion patience and enough structural stabilities; Bring difficulty for control such as smelting but contain W elements, and its expensive manufacturing cost generally do not accepted by the boiler factory (as 20～27% chromium (Cr) among the CN00803866.X, 22.5～32% nickel (Ni), 0.4～4.0% tungsten (W); Among the CN03110437.1 Cr:20% above less than 28%, Ni: greater than 35% less than 50%, W:4～10%).CN97192456.2, its room-temperature mechanical property of CN98123173.X patent steel and high temperature endurance performance and high-temperature oxidation resistance are bad, therefore can not satisfy the requirement of supercritical generating unit boiler steel.
Summary of the invention
The purpose of this invention is to provide a kind of boiler steel and manufacture method thereof, to solve the problem that existing supercritical generating unit boiler steel pipe intensity is on the low side and repeated stress failure and steam corrosion easily take place, improve the comprehensive mechanical performance of boiler steel pipe, improve the fatigue lifetime of boi1er tube, improve the resistance to overturning of generating set, further satisfy development of electric power industry.
Technical scheme of the present invention is: a kind of boiler steel is characterized in that the chemical ingredients per distribution ratio is: carbon C:0.04～0.10%, silicon Si :≤0.50%, manganese Mn :≤2.00%, nickel: 8.00～12.00%, chromium Cr:17.00～19.00%, niobium Nb:8*C～1.00%, plumbous Cu≤0.25%, sulphur S≤0.015%, phosphorus P≤0.040%, boron: 0.005～0.040%, nitrogen N:0.10～0.20%, Rare-Earth Ce: 0.005～0.100%, surplus is Fe and inevitable impurity.
Carbon: carbon is the element of strong formation and stable austenite and expansion austenitic area in austenitic stainless steel.Carbon is a kind of interstitial element, can significantly improve the intensity of austenitic stainless steel by solution strengthening.Guarantee the necessary certain carbon content of certain intensity, but carbon is too high unfavorable to intergranular corrosion, control 0.04～0.10% carbon content can proof strength require can satisfy the intergranular corrosion requirement again.
Manganese: in Chromiumnickel Austenite Stainless Steel, manganese content general provision is no more than 2.0%.Manganese can also improve the solubleness of nitrogen in steel, manganese and sulphur have stronger avidity to form manganese sulfide, promptly help the removal of sulphur in the steel, help eliminating the deleterious effect of residual sulfur in the steel again, the content of manganese is controlled at 0.80～1.60% can bring into play good effect in steel of the present invention.
Silicon: in austenitic stainless steel, silicone content is generally all below 0.8%～1.0%.Silicon is ferrite former, to forming austenite bad influence is arranged, and along with the raising of silicone content, delta ferrite level will increase in austenitic stainless steel, and intermetallic phase also can be quickened and be increased such as the formation of σ (x) phase simultaneously.Thereby influence the performance of steel.Controlling lower silicone content can make Chromiumnickel Austenite Stainless Steel have good intergranular corrosion resistance performance.Therefore the content to element silicon be controlled at≤0.50% comparatively reasonable.
Chromium: chromium is that stainless steel obtains rustless property and corrosion proof topmost element, and chromium has promoted the passivation of steel and made steel keep stablizing passive result.Chromium is again to form strongly and stablize ferritic element, dwindles the austenitic area.Raising chromium content is useful to the intergranular corrosion and the resistance of oxidation of austenitic stainless steel.Consider that stainless corrosion resistance nature guarantees that steel at room temperature is austenite structure simultaneously again, steel design chromium content of the present invention is 17.00～19.00%.
Nickel: be the main alloy element in the austenitic stainless steel, it mainly acts on is to form and stable austenite, makes steel obtain complete austenitic tissue, thereby makes steel have good intensity and plasticity, flexible cooperate.Chromium nickel can improve the heat resistance of steel.8.00～12.0% nickel can play above-mentioned beneficial effect.
Niobium: be to add, form carbide and produce dispersion-strengthened, can improve heat resistance, make chromium enter matrix more, thereby strengthen the ability of anti intercrystalline corrosion, take place to prevent the intergranular corrosion of sensitization attitude as stabilizing element.Therefore the niobium of 8*C～1.00% is the suitable content of steel of the present invention.
Nitrogen: be the important alloying element in the Chromiumnickel Austenite Stainless Steel, but except that instead of part nickel to save the valuable nickel element, mainly be intensity and the corrosion resistance nature that improves austenitic stainless steel as the solution strengthening element.Consider that from cold and hot working performance, fatigue property and high-temperature corrosion resistance performance the nitrogen of steel adding 0.10～0.20% of the present invention is only content.
Rare earth: it is effectively improving hot workability in austenitic stainless steel, also can improve the oxidation-resistance of high temperature steel.The rare earth of adding 0.005～0.100% can play above-mentioned beneficial effect.
Boron: add trace B and can improve the intergranular corrosion resistance performance, also can improve the thermoplasticity of austenitic stainless steel, improve hot workability.0.005～0.100% rare earth and 0.005～0.040% boron can play good grain-boundary strengthening effect, improve creep rupture strength and creep rupture life.
Sulphur, phosphorus, lead, antimony, bismuth should reduce its content as far as possible under technical qualification permission situation simultaneously, to reduce the poly-partially of original austenite crystal prevention place, improve toughness.Residual element and gas content are controlled at suitable low levels level, make steel have quite high purity, be dissolved in and reach the best proportioning content of ideal between carbon in the austenite and each element, thus for the homogeneity that improves material and when long enduring quality lay a good foundation.
A kind of manufacture method of boiler steel, the technical process of employing is: electric arc furnace just refines → AOD refining → die casting → 800 milling train breaking down cogging → 550 open-train mills or bar continuous rolling unit hot-rolled tube billet → tubulation → solution treatment; Or electric arc furnace just refines → AOD refining → continuous casting → 550 open-train mills or bar continuous rolling unit hot-rolled tube billet → tubulation → solution treatment.
(1) electric arc furnace just refines → AOD refining → die casting:
Carrying out molten steel in 20～60 tons electric arc furnace just refines; The ladle refining of corresponding tonnage; Die casting is poured into a mould, and produces the qualified die casting side ingot of 2.3t or 3.7t;
(2) breaking down cogging:
Adopt steel ingot heat to send mode to carry out the breaking down cogging at 800 milling trains, earlier the ingot casting that composition is qualified waters and finishes after 2 hours the demoulding and deliver to breaking down and add thermal pit, again with its hot-work rolling-cogging to 220 side: 1230～1270 ℃ of soaking temperatures, heat tracing time 〉=4.5 hour, 1200～1240 ℃ of steel ingot tapping temperatures, the male and female face temperature difference≤30 ℃;
(3) hot-rolled tube billet:
Adopt rolling mill hot-work rolling method, earlier qualified cogged ingot surface is cleared up, again its hot-work is rolling to the finished product pole: 1220～1280 ℃ of soaking temperatures, heat tracing time 〉=2.5 hour, 1200～1260 ℃ of steel billet tapping temperatures, the male and female face temperature difference≤30 ℃; (conventional austenitic stainless steel soaking temperature is 1140～1180 ℃, soaking time 2.5 hours, 1140～1180 ℃ of tapping temperatures), this steel billet soaking temperature has guaranteed tissue, performance and the surface quality of pole effectively;
(4) tubulation:
Pipe material examination → centering → peeling → surface check → fracture → heating → perforation → pickling check → tack tail → lubricated → rolling → deoil → anneal → align → Pipe Cutting → pickling → lubricated → rolling → deoil → finished product thermal treatment → aligning → Pipe Cutting → pickling → check (ultrasonic wave, surface) → cut scale → finished product cleaning → surface check → packing to put in storage;
(5) production tube carries out solution treatment: 1140 ℃～1180 ℃ of solid solubility temperatures, soaking time (walking speed) is adjusted water-cooled according to the wall thickness difference.
The manufacture method of described boiler steel is characterized in that also comprising following steps:
(1) electric arc furnace just refines → AOD refining → continuous casting:
(2) hot-rolled tube billet:
Adopt rolling mill hot-work rolling method, earlier qualified continuously cast bloom surface is cleared up, again its hot-work is rolling to the finished product pole: 1220～1280 ℃ of soaking temperatures, heat tracing time 〉=2.5 hour, 1200～1260 ℃ of steel billet tapping temperatures, the male and female face temperature difference≤30 ℃;
(3) tubulation;
(4) production tube carries out solution treatment: 1140 ℃～1180 ℃ of solid solubility temperatures, soaking time is adjusted according to the wall thickness difference, water-cooled.
Preferably, in the manufacture method of described boiler steel, the AOD refining is AOD+VOD+LF or AOD+LF in the step (1).
The present invention compared with prior art has following beneficial effect:
1, reduces nickel content, cost of alloy is reduced, effectively saved nickel resources.
2, rolled stainless steel of the present invention becomes bar to become steel pipe with cold rolling, sample after solution treatment, tensile strength 〉=650MPa, yield strength 〉=270MPa, elongation 〉=40%, relative reduction in area 〉=60%.
3, the rational proportion of chemical ingredients had both guaranteed that its cost was lower, guaranteed that again its cold and hot working performance is not less than existing 1Cr19Ni11Nb austenitic stainless steel; Add rare earth simultaneously and nitrogen content comes guaranteed performance at joint nickel, make it that favorable tissue stability and hot and cold processing characteristics be arranged.
4, welding property is good: the good mechanical performance of commissure has good anti-steam oxidation and heat-resistant anti-fatigue characteristic simultaneously.
Embodiment
The technical process that the preparation method adopts is: 1, electric arc furnace just refines → AOD refining → die casting; 2,800 milling train breaking down coggings; 3,550 open-train mills or bar continuous rolling unit hot-rolled tube billet.
The concrete chemical ingredients of embodiment (weight percent wt%) sees Table 1, and main technologic parameters control sees Table 2, and the Performance Detection index sees Table 3, table 4.
Table 1 chemical ingredients (wt%)
| Embodiment | C | Si | Mn | P | S | Ni | Cr | Cu | Nb | N | B (add-on) | Rare earth (Ce add-on) |
| 1 | 0.0 55 | 0.40 | 1.0 9 | 0.02 7 | 0.006 | 10.96 | 18.90 | 0.25 | 0.55 | 0.11 | 0.008 | 0.030 |
| 2 | 0.0 69 | 0.32 | 1.1 6 | 0.02 3 | 0.004 | 11.50 | 17.02 | 0.23 | 0.68 | 0.10 | 0.010 | 0.100 |
| 3 | 0.0 90 | 0.21 | 0.7 3 | 0.01 5 | 0.008 | 10.20 | 17.59 | 0.22 | 0.84 | 0.12 | 0.015 | 0.080 |
| 4 | 0.0 75 | 0.31 | 1.1 7 | 0.02 4 | 0.004 | 9.74 | 17.96 | 0.22 | 0.69 | 0.15 | 0.010 | 0.015 |
| 5 | 0.0 70 | 0.29 | 1.1 4 | 0.02 5 | 0.005 | 9.00 | 18.59 | 0.24 | 0.68 | 0.20 | 0.015 | 0.042 |
| 6 | 0.0 42 | 0.48 | 1.8 0 | 0.03 8 | 0.014 | 11.90 | 18.02 | 0.20 | 0.40 | 0.18 | 0.024 | 0.008 |
| 7 | 0.0 96 | 0.12 | 0.5 2 | 0.03 2 | 0.010 | 8.30 | 17.55 | 0.18 | 0.96 | 0.15 | 0.035 | 0.062 |
| Compared steel | 0.0 69 | 0.32 | 1.1 6 | 0.02 3 | 0.004 | 11.30 | 17.52 | 0.23 | 0.68 | － | － | － |
Table 2 main technologic parameters
Table 3 room-temperature mechanical property
| Embodiment | Tensile strength Rm (MPa) | Yield strength Rp0.2 (MPa) | Elongation A (%) | Relative reduction in area Z (%) 5 |
| 1 | 685 | 280 | 52.00 | 68.00 |
| 2 | 690 | 285 | 47.87 | 69.75 |
| 3 | 720 | 300 | 45.41 | 66.82 |
| 4 | 750 | 325 | 48.10 | 68.19 |
| 5 | 735 | 305 | 47.56 | 67.9610 |
| 6 | 725 | 315 | 46.50 | 65.00 |
| 7 | 740 | 335 | 47.00 | 66.50 |
| Compared steel | 585 | 235 | 50.84 | 68.70 |
Table 4 enduring quality relatively
| Embodiment | Temperature (℃) | Stress (MPa) | Rupture time (h) | Elongation (%) | Relative reduction in area (%) |
| 1 | 750 | 120 | 219:05 | 45.0 | 50.0 |
| 2 | 750 | 120 | 208:09 | 27.3 | 45.6 |
| 3 | 750 | 120 | 258:11 | 33.0 | 35.0 |
| 2 | 750 | 120 | 208:09 | 27.3 | 45.6 |
| 4 | 750 | 120 | 290:23 | 15.5 | 26.0 |
| 5 | 750 | 120 | 367:01 | 13.0 | 22.5 |
| 6 | 750 | 120 | 359：23 | 14.0 | 21.5 |
| 7 | 750 | 120 | 311：42 | 15.5 | 23.0 |
| Compared steel | 750 | 120 | 104:04 | 26.0 | 41.6 |
Implement the hot rolling pole that the present invention produces, room-temperature mechanical property and high temperature endurance performance are apparently higher than compared steel (1Cr19Ni11Nb), improve the work-ing life of high pressure boiler tube, particularly crucial realistic meaning is arranged for solving the high pressure boiler tube oxidation-resistance.
Claims (3)
1. the manufacture method of a boiler steel is characterized in that comprising following steps:
(1) electric arc furnace just refines → AOD refining → die casting, and the chemical element quality per distribution ratio of control boiler steel is C 0.04～0.10%, Si≤0.50%, Mn≤2.00%, Ni 8.00～12.00%, and Cr 17.00～19.00%, 8 times～1.00% of Nb C constituent content, Cu≤0.25%, S≤0.015%, P≤0.040%, B 0.005～0.040%, N 0.10～0.20%, and Ce 0.005～0.100%, and surplus is Fe and inevitable impurity;
(2) breaking down cogging: breaking down cogging, 1230～1270 ℃ of soaking temperatures, heat tracing time 〉=4.5 hour, 1200～1240 ℃ of steel ingot tapping temperatures, the male and female face temperature difference≤30 ℃;
(3) hot-rolled tube billet: adopt rolling mill hot-work rolling method, earlier qualified cogged ingot surface is cleared up, again its hot-work is rolling to the finished product pole: 1220～1280 ℃ of soaking temperatures, heat tracing time 〉=2.5 hour, 1200～1260 ℃ of steel billet tapping temperatures, the male and female face temperature difference≤30 ℃;
(4) tubulation;
(5) production tube carries out solution treatment: 1140 ℃～1180 ℃ of solid solubility temperatures, soaking time is adjusted according to the wall thickness difference, water-cooled.
2. the manufacture method of a boiler steel is characterized in that comprising following steps:
(1) electric arc furnace just refines → AOD refining → continuous casting, and the chemical element quality per distribution ratio of control boiler steel is C 0.04～0.10%, Si≤0.50%, Mn≤2.00%, Ni 8.00～12.00%, and Cr 17.00～19.00%, 8 times～1.00% of Nb C constituent content, Cu≤0.25%, S≤0.015%, P≤0.040%, B 0.005～0.040%, N 0.10～0.20%, and Ce 0.005～0.100%, and surplus is Fe and inevitable impurity;
(2) hot-rolled tube billet: adopt rolling mill hot-work rolling method, earlier qualified continuously cast bloom surface is cleared up, again its hot-work is rolling to the finished product pole: 1220～1280 ℃ of soaking temperatures, heat tracing time 〉=2.5 hour, 1200～1260 ℃ of steel billet tapping temperatures, the male and female face temperature difference≤30 ℃;
(3) tubulation;
(4) production tube carries out solution treatment: 1140 ℃～1180 ℃ of solid solubility temperatures, soaking time is adjusted according to the wall thickness difference, water-cooled.
3. the manufacture method of boiler steel as claimed in claim 1 or 2 is characterized in that: the AOD refining is AOD+VOD+LF or AOD+LF in the step (1).
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| CN2007100449504A CN101368249B (en) | 2007-08-17 | 2007-08-17 | Steel for boiler and method of producing the same |
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| CN101368249B true CN101368249B (en) | 2010-08-11 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101967610B (en) * | 2009-07-28 | 2012-07-04 | 宝山钢铁股份有限公司 | High carbon high silicon martensite stainless steel billet and preparation method thereof |
| CN102383025B (en) * | 2011-10-13 | 2013-03-06 | 中核苏阀横店机械有限公司 | Preparation method of super-critical high alloy steel suitable for thermal power unit |
| CN103540860A (en) * | 2013-09-27 | 2014-01-29 | 泰州永兴合金材料科技有限公司 | High-strength and corrosion-resistant stainless steel plate |
| CN105296887A (en) * | 2015-12-09 | 2016-02-03 | 江苏东方电力锅炉配件有限公司 | Boiler tube and manufacturing process thereof |
| CN106939390B (en) * | 2017-03-31 | 2018-06-19 | 哈尔滨汽轮机厂有限责任公司 | Supercritical turbine valve hole part deformation strengthening Austenitic stainless steel forging material |
| CN108660358A (en) * | 2018-06-08 | 2018-10-16 | 本钢板材股份有限公司 | A kind of production technology of boiler heat resisting structural steel 12Cr1MoV |
| CN114606441A (en) * | 2022-02-28 | 2022-06-10 | 浙江瑞浦科技有限公司 | Free-cutting stainless steel wire rod capable of being drawn into hexagonal bright rod at one time and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871368A (en) * | 2003-10-20 | 2006-11-29 | 株式会社久保田 | Heat-resistant cast steel for reaction tube for hydrogen production being excellent in aging ductility and creep rupture strength |
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| CN1871368A (en) * | 2003-10-20 | 2006-11-29 | 株式会社久保田 | Heat-resistant cast steel for reaction tube for hydrogen production being excellent in aging ductility and creep rupture strength |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2007-186727A 2007.07.26 |
| JP特开平9-195005A 1997.07.29 |
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Effective date of registration: 20140122 Address after: No. 1269, Fisheries Road, Shanghai, Baoshan District, China Patentee after: BAOSTEEL SPECIAL STEEL Co.,Ltd. Address before: 201900 Fujin Road, Shanghai, orchard, Baoshan District Patentee before: BAOSHAN IRON & STEEL Co.,Ltd. |
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Granted publication date: 20100811 Termination date: 20210817 |