CN101328560B - Ni seamless steel pipe and manufacturing method thereof - Google Patents
Ni seamless steel pipe and manufacturing method thereof Download PDFInfo
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- CN101328560B CN101328560B CN2007100423580A CN200710042358A CN101328560B CN 101328560 B CN101328560 B CN 101328560B CN 2007100423580 A CN2007100423580 A CN 2007100423580A CN 200710042358 A CN200710042358 A CN 200710042358A CN 101328560 B CN101328560 B CN 101328560B
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Abstract
The invention relates to a nickel-based seamless steel pipe which comprises the following compositions in percentage by weight: 0.05 to 0.15 percent of C, 0.20 to 0.35 percent of Si, 0.35 to 0.60 percent of Mn, 3.20 to 3.80 percent of Ni, 0.01 to 0.3 percent of Cu, 0.01 to 0.4 percent of Mo, 0.001 to 0.05 percent of Ti, 0.01 to 0.1 percent of V, 0.005 to 0.039 percent of Al, less than or equal to 0.015 percent of P, less than or equal to 0.008 percent of S, less than or equal to 0.01 percent of O, less than or equal to 0.004 percent of N, the balance being Fe and inevitable impurities; and the ratio of Ca to S is more than or less than 1. The method for manufacturing the nickel-based seamless steel pipe comprises the following steps that: a pipe blank produced by continuous casting or continuous rolling is heated at a temperature of between 1180 and 1280 DEG C, rolled and separated from a bar mold at a temperature of between 950 and 1050 DEG C, is sent to a reheating furnace, is kept at a temperature of between 850 and 1000 DEG C, is subjected to rolling, air cooling at a cooling speed of between 10 and 30 DED C/min, kept at a temperature of between 800 and 900 DEG C, tempered, kept at a temperature of between 600 and 700 DEG C and tempered, thereby manufacturing a finished pipe. The nickel-based seamless steel pipe can be used for impacting a pressure container with a toughness of more than or equal to 18 J under the conditions of having a low temperature of between 80 and 101 DEG below zero and containing methanol and other corrosion mediums.
Description
Technical field
The present invention relates to metal material field, especially a kind of Ni is weldless steel tube and manufacture method thereof, particularly at-80 ℃～-101 ℃ low temperature, contain under the corrosive medium conditions such as methyl alcohol simultaneously, the pressurized vessel of impelling strength 〉=18J is weldless steel tube and manufacture method thereof with Ni.
Background technology
At present, domestic ethylene cracker under-80～-101 ℃ operating condition, need with Ni be weldless steel tube, because its consumption on a cover cracker is few, specification is many, even import is also relatively more difficult in the buying, and domestic like product low-temperature flexibility instability, therefore, generally adopt stainless steel tube such as TP304 to substitute.
Along with the petrifaction ethylene cracker develops to maximization and high-load direction, because of the yield strength of TP304 low, need to increase wall thickness and guarantee its yield strength, reduced the heat exchanger effectiveness of equipment, therefore use 3.5%Ni weldless steel tube just to seem to have advantage with good low-temperature flexibility.Because the 3.5%Ni weldless steel tube belongs to the high product of added value, the weldless steel tube manufacturing firm of product development and production technique comparative maturity as the composition of SUMITOMO CHEMICAL steel pipe is all abroad: C0.055, Si0.18, Mn0.56, P0.009, S0.005, Cr0.04, Ni3.58, Mo0.11, V＜0.01, Ti＜0.01, Nb＜0.01, A10.040 (annotate: this is the measured result that the product material object is analyzed).
Domestic have only the seamless energy in Chengdu to produce, but because of research and development of products initial stage low-temperature impact toughness instability, therefore, be not applied on-80 ℃～-101 ℃ petrochemical industry cryogenic units always.Cryogenic unit with weldless steel tube in use occur such as purchasing problem and reduce the thermo-efficiency problem production bring suitable inconvenience and caused the certain economic loss to petrochemical industry.
It is very high that low temperature is that with the production difficulty of 3.5%Ni weldless steel tube it requires low-temperature impact toughness, and this has just determined chemical ingredients, purity, rolling technique and heat treating regime to steel all to propose very high requirement.
Influence material at low temperature flexible principal element carbon equivalent, The amount of inclusions and form, metallographic structure and segregation and hardness etc. are arranged.Carbon equivalent is high more, inclusion is many more and form is irregular more, segregation is serious more, hardness is high more, metallographic structure is complicated more, and its low-temperature performance is poor more.
The quantity of inclusion and form can be handled by smelting and calcium and control, and hardness and segregation generally need be controlled by reducing carbon equivalent.But along with the reduction of carbon equivalent, the intensity of material also can reduce.For guaranteeing under the condition of low-carbon-equivalent, to obtain enough intensity, in Steel Plates For Low Temperature Service is produced, can pass through the mode of controlled rolling and controlled cooling (TMCP), utilize working hardening to improve intensity.But in the production of weldless steel tube, because last finisher deflection is very little, so can not rely on the TMCP mode to improve product strength fully.Be proof strength, need to improve the carbon equivalent of material,, be difficult to guarantee the postwelding low-temperature flexibility in case improved carbon equivalent.For addressing this problem, the domestic producer that has once attempted producing steel plate by the mode of quenching+intercritical hardening+tempering heat treatment.After having adopted this heat treatment mode, can adopt the material of low-carbon-equivalent, and after the thermal treatment, the homogeneity of structure of material is greatly improved, thereby guarantees that material has higher intensity and low-temperature impact toughness.
Quench again after but steel pipe rolls+intercritical hardening+tempered thermal treatment, for normalizing+tempering, increased the difficulty that tissue is produced, increased production cost, not only bring certain difficulty, and can reduce the competitiveness of product in market to production.
Chinese patent application 200410037809.8 steel belong to field of welding material, and it is used greater than the steel of 780MPa level to be specially adapted to welding buckling strength, have the welding electrode of good low-temperature toughness and higher-strength.This welding electrode mainly guarantees that by adding Ni and Cu welding electrode has good low-temperature toughness and higher-strength, when adopting this welding electrode to weld, can improve the yield strength and the low-temperature flexibility of deposited metal effectively, has good comprehensive mechanical property.
The clear 63-130245A steel of Japanese Patent Application Laid-Open, in order to guarantee that Ni is that steel plate has good toughness in low temperature steel plate centre, by a plate that special chemical constitution arranged and etc. the casting of crystalline speed, super low loading by control P, hot rolling and thermal treatment then, thereby the highly effective and safe of assurance cold condition lower steel plate.It relies on the performance of tooling to guarantee the low-temperature flexibility in steel plate centre fully, the existing steel-making equipment of Baosteel does not possess the working condition of the low P steel of this smelting, and trace element is few in the invar, under existing tube rolling equipment condition, is difficult to control close grain and banded structure.And produce steel plate and can adopt the method for controlled rolling and controlled cooling to come guaranteed performance, and last procedure of tubulation is to open to subtract, it is little that deflection rolls plate relatively, do not reach the level of the controlled rolling and controlled cooling that rolls plate.In other words, this composition does not possess the tube rolling condition under Baosteel existing weaponry and equipment condition.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of low temperature weldless steel tube new steel grade and manufacture method thereof, the content of the C of this steel grade, Si, Mn, P, S, Ni element satisfies standard-required, and trace elements such as the V that is added, Nb, Cu, A1 are different from the Sumitomo product; Behind steel pipe rolling, do not need quenching+intercritical hardening+tempering heat treatment, but in the operation of rolling, the control finishing temperature, controlled chilling speed, product reaches more than the 350Mpa through guaranteeing the weldless steel tube yield strength after normalizing+temper, simultaneously can satisfy the requirement of-100 ℃ of low-temperature flexibility 〉=18J again, and have good welding property.
Ni of the present invention is a weldless steel tube, adopts following composition (wt%):
C：0.05～0.15％
Si：0.20～0.35％
Mn：0.35～0.60％
Ni：3.20～3.80％
Cu：0.01～0.3％
Mo：0.01～0.4％
Ti：0.001～0.05％
Al：0.005～0.039％
V：0.01～0.1％
P：≤0.015％
S：≤0.008％
O：≤0.01％
N：≤0.004％
Steel is handled through calcium in smelting, Ca/S 〉=1
All the other are Fe and unavoidable impurities.
Ni according to the present invention is a weldless steel tube, can also add Nb:0.01～0.05%, one or both in Cr:0.009～0.03% on the basis of mentioned component.。
Ni of the present invention is the manufacture method of weldless steel tube, in turn includes the following steps:
The pipe that obtains by continuous casting or tandem rolling 1180～1280 ℃ after the rotary heating furnace heating, make pipe behind austenitizing, obtain evenly tiny single-phase austenite structure, austenite is the sosoloid of carbon in γ-Fe, have face-centered cubic lattice, its plasticity is good, easy deformation.Under the single phase structure condition, bore a hole through tapping machine, then at 950～1050 ℃ of tube rollings, enter reheating furnace after taking off rod, after 850～1000 ℃ of insulations, enter the rolling back of stretch-reducing mill or elongator air cooling, need controlled chilling speed, span of control temperature drop speed is 10～30 ℃/minute, carries out normalizing 800～900 ℃ of insulations, carries out tempering 600 ℃～700 ℃ insulations then and makes production tube.
Steel grade of the present invention, produce in existing weaponry and equipment condition undertissue, higher structure stability is arranged, can guarantee steel pipe under normalizing+tempered condition grain fineness number more than 10 grades, banded structure is less than 2.5 grades, yield strength can satisfy needed toughness reguirements under-80 ℃～-101 ℃ low temperature fully more than 350Mpa.
The characteristics that Ni according to the present invention is a weldless steel tube are:
C:0.05～0.15% (wt%, below each element identical), C is a carbide forming element, for general structure iron, suitably increase the intensity that carbon content can improve steel, reduce the anufacturability that carbon content can obviously be improved steel pipe, DeGrain when content is too low, too Gao Shihui reduces the low-temperature flexibility of steel greatly, also can reduce the welding property of steel simultaneously.
Si:0.20～0.35% mainly is by the remarkable reinforced ferrite of solid solution energy in ferrite, improves the intensity of steel, will reduce the low-temperature flexibility of steel during the Si too high levels, and toughness-brittle transition temperature is raise.
Mn:0.35～0.60%, Mn are austenite former, can improve the intensity of steel, and content is not obvious less than effect in 0.35% o'clock, and content surpasses at 0.60% o'clock, and the microstructure segregation tendency increases the weight of, the homogeneity of influence tissue, thus reduce low-temperature flexibility.
Mo:0.01～0.4%: mainly be the intensity that improves steel by the form that forms carbide and solution strengthening, too high levels can reduce the toughness and the welding property of steel.
V:0.010～0.100% mainly plays the precipitation strength effect, and can crystal grain thinning, forms carbide, improves the intensity and the toughness of steel.Suitable vanadiumcontent can also improve the weldability and the smelting technology of steel, but content is when reaching a certain amount of, and its effect increase is just not obvious.
Ti:0.001～0.050% can produce precipitation strength and crystal grain thinning effect, forms carbide, improves the intensity and the toughness of steel.But when content reached a certain amount of, its effect increase was just not obvious.
Al:0.005～0.039% is rationally controlled Al content, and Al exists with carboritride or solid solution condition.The gap that Al and N form stabilizer pole and exists with tiny particle mutually, produces dispersion-strengthened effect.AlN can effectively stop AUSTENITE GRAIN COARSENING, improves the toughness of steel.
Nb:0.010～0.050% can crystal grain thinning, forms carbide, improves the intensity and the toughness of steel.But when content reached a certain amount of, its effect increase was just not obvious.
Cu:0.01～0.30% can improve the homogeneity of structure of steel, and it is not obvious to add too low effect, adds the fragility that can increase steel too much.
Ni:3.20～3.80% cooperates Cu to add, and can improve the low-temperature flexibility of steel, adds too lowly or too high, acts on not obvious.
S :≤0.008%, rationally control its content, otherwise can increase sulfide content, influence the low-temperature flexibility of steel.
P :≤0.015%, rationally control its content, otherwise can increase microstructure segregation, influence the low-temperature flexibility of steel.
O :≤0.01%, rationally control its content, otherwise will improve brittle transition temperature greatly, reduce plasticity, oxygen forms inclusion in metallic matrix simultaneously, reduces the purity of steel.
N :≤0.004%, rationally control its content, otherwise low-temperature flexibility instability and cold impact value are on the low side, promptly the toughness deposit is on the low side.
Ca/S 〉=1 can make inclusion balling, improves the low-temperature flexibility of steel.
The present invention guarantees the mechanical property except that the control carbon equivalent, by adopting micro-vanadium, niobium, titanium, aluminium to come crystal grain thinning, by adding an amount of copper, improve the homogeneity of structure of steel, alleviate band shape, improve the intensity of steel by adding an amount of Mo, thereby improve the yield strength and the low-temperature flexibility of steel.
Present domestic ethylene cracker mainly adopts the TP304 stainless steel with-80 ℃～-101 ℃ low-temperature zone with pipe, the unnecessary energy waste problem that existence causes because of yield strength is low, this steel grade can be applied under the low relatively situation of cost of alloy, and there is not a unnecessary energy waste problem, can satisfy the requirement of cryogenic unit safe operation, simultaneously, under existing steel pipe manufacturing equipment condition, also be convenient to tissue production.
SUMITOMO CHEMICAL steel pipe trace element is few, analyzes from material object, and it should be to begin and rely on to make steel to equip the purity of realizing product from ore dressing, and then guarantees the low-temperature flexibility of product.Although japanese product does not add too much trace element, the cost of ore dressing is higher than the interpolation trace element in fact.
The present invention adds a certain amount of Mo, Cu on the basis of steel, rationally control V, Nb, Ti, Al trace element, temperature by the control reheating furnace is controlled finishing temperature, and controlled chilling speed, guarantee that under suitable normalizing+tempering process system all alloying elements play reinforcement and crystal grain thinning effect respectively, guarantee homogeneity of structure, alleviate microstructure segregation, make product satisfy cryogenic unit pipe requirement to intensity and low-temperature flexibility in operational process after the welding fully.
Embodiment
Further describe the characteristics and the advantage of steel grade of the present invention below by embodiment and comparative example.
Embodiments of the invention 1～8 compare with regard to chemical ingredients, mechanical property and low-temperature flexibility with the SUMITOMO CHEMICAL weldless steel tube, and its chemical ingredients sees Table 1, and mechanical property sees Table 3, and low-temperature flexibility sees Table 4.，
The preparation technology of embodiments of the invention is:
The pipe that is obtained by continuous casting or tandem rolling heats through rotary heating furnace at 1180～1280 ℃, and for example 1260 ℃, then, make pipe behind austenitizing, obtain evenly tiny single-phase austenite structure.
Under the single phase structure condition, bore a hole through tapping machine, then at 950～1050 ℃, concrete 1030 ℃ of tube rollings according to appointment enter reheating furnace after taking off rod, 850～1000 ℃ of insulations, specifically according to appointment 950 ℃, then, enter the rolling back of stretch-reducing mill or elongator air cooling, speed of cooling is controlled to be 10～30 ℃/minute, and is concrete as 27 ℃/minute.
Carry out normalizing 800～900 ℃ of insulations, carry out tempering 600 ℃～700 ℃ insulations then and make production tube.Concrete normalizing and tempering heat treatment system see Table 2.
Table 1
| Steel grade | C | Si | Mn | Mo | V | Ti | Nb | Cr | A1 | Cu | Ni |
| Embodiment 1 | 0.05 | 0.20 | 0.35 | 0.01 | 0.01 | 0.001 | 0.005 | 0.01 | 3.20 | ||
| Embodiment 2 | 0.06 | 0.23 | 0.56 | 0.097 | 0.015 | 0.001 | 0.01 | 0.009 | 0.01 | 0.02 | 3.25 |
| Embodiment 3 | 0.05 | 0.23 | 0.43 | 0.11 | 0.014 | 0.002 | 0.009 | 0.020 | 0.03 | 3.59 | |
| Embodiment 4 | 0.10 | 0.27 | 0.55 | 0.051 | 0.015 | 0.001 | 0.009 | 0.006 | 0.02 | 3.28 | |
| Embodiment 5 | 0.05 | 0.21 | 0.36 | 0.01 | 0.010 | 0.001 | 0.01 | 0.010 | 0.01 | 3.20 | |
| Embodiment 6 | 0.07 | 0.25 | 0.40 | 0.15 | 0.030 | 0.015 | 0.03 | 0.02 | 0.030 | 0.10 | 3.50 |
| Embodiment 7 | 0.12 | 0.30 | 0.50 | 0.30 | 0.070 | 0.001 | 0.04 | 0.020 | 0.20 | 3.70 | |
| Embodiment 8 | 0.15 | 0.35 | 0.60 | 0.40 | 0.10 | 0.050 | 0.05 | 0.039 | 0.30 | 3.79 | |
| Comparative Examples | 0.055 | 0.18 | 0.56 | 0.11 | <0.01 | <0.01 | <0.01 | 0.040 | 0.040 | 3.58 |
Table 2
| Normalizing, ℃ | Tempering, ℃ | |
| Embodiment 1 | 900 | 700 |
| Normalizing, ℃ | Tempering, ℃ | |
| Embodiment 2 | 880 | 680 |
| Embodiment 3 | 860 | 660 |
| Embodiment 4 | 850 | 640 |
| Embodiment 5 | 850 | 640 |
| Embodiment 6 | 840 | 620 |
| Embodiment 7 | 820 | 620 |
| Embodiment 8 | 800 | 600 |
| Comparative Examples | 870 | 620 |
Table 3
| Steel grade | Yield strength, MPa | Tensile strength, MPa | Elongation, % |
| Embodiment 1 | 400 | 450 | 36.5 |
| Embodiment 2 | 395 | 550 | 33.5 |
| Embodiment 3 | 360 | 480 | 42.0 |
| Embodiment 4 | 370 | 510 | 35.5 |
| Embodiment 5 | 400 | 480 | 37.0 |
| Embodiment 6 | 395 | 500 | 36.0 |
| Embodiment 7 | 405 | 512 | 36.5 |
| Embodiment 8 | 410 | 500 | 32.5 |
| Comparative Examples | 398 | 588 | 35 |
Table 4
As seen the stable mechanical property of steel grade of the present invention, low-temperature performance is good.
The present invention is under Baosteel existing weaponry and equipment condition, by suitable interpolation trace element, control S, P, O, N content, the content and the inclusion modification of control inclusion are handled, guarantee that under suitable rolling technology and normalizing+tempering heat treatment process system all alloying elements play reinforcement and crystal grain thinning effect respectively, guarantee homogeneity of structure, alleviate banded segregation, steel grade of the present invention is satisfying cryogenic unit pipe requirement to intensity and low-temperature flexibility in operational process fully after the welding under Baosteel existing weaponry and equipment condition.
Though abovely the present invention has been carried out describing in detail by embodiment, be not limited only to these embodiment, other embodiment of more equivalences can also be arranged under the prerequisite that does not break away from design of the present invention, scope of the present invention is determined by claims.
Claims (9)
1. a nickel is weldless steel tube, and the weight percent of its component is:
C：0.05～0.15％
Si：0.20～0.35％
Mn：0.35～0.60％
Ni：3.20～3.80％
Cu：0.01～0.3％
Mo：0.01～0.4％
Ti：0.001～0.05％
V：0.01～0.1％
Al：0.005～0.039％
P：≤0.015％
S：≤0.008％
O：≤0.01％
N：≤0.004％
Ca/S≥1
All the other are Fe and unavoidable impurities.
2. nickel according to claim 1 is weldless steel tube, it is characterized in that, its component also comprises Nb:0.01～0.05% of weight percent meter, one or both in Cr:0.009～0.03%.
3. claim 1 or 2 described nickel are weldless steel tube, it is characterized in that, its yield strength is more than the 350Mpa ,-100 ℃ of low-temperature flexibility 〉=18J.
4. each described nickel is the purposes of weldless steel tube in pressurized vessel in the claim 1～3.
5. the described purposes of claim 4 is characterized in that, described nickel is that weldless steel tube is used for-80 ℃～-101 ℃ low temperature, contains under the methyl alcohol corrosive medium condition pressurized vessel of impelling strength 〉=18J simultaneously.
6. be the manufacture method of weldless steel tube as the described nickel of one of claim 1～5, in turn include the following steps:
A. the pipe that is obtained by continuous casting or tandem rolling is 1180～1280 ℃ of heating;
B. at 950～1050 ℃ of tube rollings, take off rod;
C. enter reheating furnace, 850～1000 ℃ of insulations;
D. be rolled the back air cooling, speed of cooling is 10～30 ℃/minute;
E. carry out normalizing 800～900 ℃ of insulations;
F. carry out tempering 600 ℃～700 ℃ insulations;
Make production tube.
7. nickel according to claim 6 is the manufacture method of weldless steel tube, it is characterized in that, described pipe heats at rotary heating furnace.
8. nickel according to claim 6 is the manufacture method of weldless steel tube, it is characterized in that, before carrying out the b step, makes described pipe behind austenitizing, bores a hole through tapping machine.
9. nickel according to claim 6 is the manufacture method of weldless steel tube, it is characterized in that, in described d step, enters stretch-reducing mill or elongator is rolled through the pipe behind the c step heat tracing.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407426A (en) * | 2010-09-26 | 2012-04-11 | 上海月月潮钢管制造有限公司 | Method for manufacturing low alloy steel tube of low-temperature pressure vessel |
| CN102691006B (en) * | 2011-03-23 | 2013-12-25 | 宝山钢铁股份有限公司 | High tempering parameter SR embrittlement resistant cryogenic nickel steel and manufacture method thereof |
| CN102434725B (en) * | 2011-10-10 | 2016-05-25 | 江西金盈新材料科技股份有限公司 | A kind of manufacture method of large-caliber stainless steel seamless pipe |
| CN103131963B (en) * | 2013-03-22 | 2016-01-13 | 内蒙古包钢钢联股份有限公司 | The low temperature preparation method of weldless steel tube material |
| CN104818425A (en) * | 2015-04-02 | 2015-08-05 | 衡阳华菱钢管有限公司 | Minor-caliber 9Ni seamless steel pipe for low-temperature service and production method thereof |
| CN105177452B (en) * | 2015-09-08 | 2017-03-22 | 山东钢铁股份有限公司 | Alloy steel plate for pressure container and preparation method thereof |
| CN105349886B (en) * | 2015-12-03 | 2017-08-29 | 攀钢集团成都钢钒有限公司 | 195 DEG C of used at ultra-low temperature seamless steel pipes and preparation method thereof |
| CN108660385A (en) * | 2017-03-30 | 2018-10-16 | 宝山钢铁股份有限公司 | A kind of low-alloy steel of acid corrosion-resistant, steel pipe, steel plate and its manufacturing method |
| CN112251662A (en) * | 2020-08-25 | 2021-01-22 | 常熟市虹桥铸钢有限公司 | High-strength high-toughness low-alloy steel and heat treatment method thereof |
| CN114351044A (en) * | 2021-12-02 | 2022-04-15 | 包头钢铁（集团）有限责任公司 | Rare earth treatment low-temperature pipeline and production method thereof |
| CN114645183B (en) * | 2022-03-26 | 2023-01-03 | 湖南华菱湘潭钢铁有限公司 | Production method of high-toughness low-yield-ratio low-alloy high-strength steel plate |
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| CN1529765A (en) * | 2000-08-07 | 2004-09-15 | 埃克森美孚上游研究公司 | Weld metals with superior low temperature toughness jfor joining high strength, low alloy steels |
| CN1946862A (en) * | 2004-04-07 | 2007-04-11 | 新日本制铁株式会社 | Thick high strength steel plate having excellent low temperature toughness in welding heat affected zone caused by high heat input welding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1529765A (en) * | 2000-08-07 | 2004-09-15 | 埃克森美孚上游研究公司 | Weld metals with superior low temperature toughness jfor joining high strength, low alloy steels |
| CN1946862A (en) * | 2004-04-07 | 2007-04-11 | 新日本制铁株式会社 | Thick high strength steel plate having excellent low temperature toughness in welding heat affected zone caused by high heat input welding |
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