CN104313474A - Seamless steel tube for rare earth containing low-cost H2S corrosion-resistant L320NS pipeline and production method thereof - Google Patents
Seamless steel tube for rare earth containing low-cost H2S corrosion-resistant L320NS pipeline and production method thereof Download PDFInfo
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- CN104313474A CN104313474A CN201410620607.XA CN201410620607A CN104313474A CN 104313474 A CN104313474 A CN 104313474A CN 201410620607 A CN201410620607 A CN 201410620607A CN 104313474 A CN104313474 A CN 104313474A
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Abstract
The invention relates to a seamless steel tube for a rare earth containing low-cost H2S corrosion-resistant L320NS pipeline and a production method thereof. The production method comprises the following steps: carrying out pretreatment on blast furnace molten iron, so that the S content of the blast furnace molten iron is reduced below 0.010% by mass percent; adding the treated blast furnace molten iron and steel scrap to a top-bottom combined blowing converter for smelting, adopting deoxidation alloy in the steel tapping process for deoxidation alloying, carrying out final deoxidation by adopting an aluminum deoxidation technology, carrying out slag blocking or deslagging in the steel tapping process, adding lime blocks after adding the alloy in the steel tapping process, then adding the smelted molten iron to an LF (Ladle Furnace) for refining, blowing argon during refining, and heating for warming in a manner of gradually increasing the warming speed; then carrying out slag making, desulfurization, composition adjustment and warming operations; adopting the operation of white slag making, and adding ferromolybdenum alloy, ferrocolumbium alloy and ferrotitanium alloy; finally continuously blowing argon gas softly at the bottom, adding rare earth wires, and then carrying out VD (Vacuum Distillation) vacuum treatment, round billet continuous casting, tube blank heating, perforating, continuous rolling, reheating, sizing, straightening, cooling, saw cutting, flaw detection and chamfering.
Description
Technical field
The invention belongs to ferrous metal smelting and metal-pressed machine field, relate to a kind of containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe and production method thereof.
Background technology
Features such as pipeline transportation has economical and efficient because of it, uninterrupted and pollution-free and being used widely, in order to realize the long apart from transport of pipeline, need Hi-grade steel line pipe, because part in China's hydrocarbon resources exists water and H
2s gas, this brings serious etching problem to transport pipe, and is difficult to prediction.Low Temperature Wet hydrogen sulfide corrosion mainly contains stress corrosion (SSC) and hydrogen induced cracking (HIC) (HIC) two kinds of collapse modes.These two kinds of collapse modes all produced serious accident in Oil and Natural Gas Transportation Pipeline.For this reason, moisture-resistant H is in succession developed both at home and abroad
2s corroded pipeline pipe, the application of these materials effectively prevents generation and the destruction of Wet hydrogen sulfide corrosion.
Through retrieval, Chinese invention patent " a kind of Ultra-low carbon high tenacity anti-H 2 S steel for gas delivering pipeline " (number of patent application: CN 1351189A), there is following problem and shortcoming in it:
Impurity element Cu (% by weight≤0.20%) content is high.This is the deficiency that raw material electric furnace production technique cannot overcome with steel scrap, because the fusing point of Cu element is low, this can give smelt, the operation of rolling cause certain difficulty.
Summary of the invention
The object of this invention is to provide that a kind of production cost is low, toughness and tenacity coupling is high, crystal grain is tiny, resistance to H
2what S stress corrosion performance was high contains rare earth low cost seamless steel pipe for line pipe and production method thereof.
To achieve these objectives, the present invention's one is containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe, and described weldless steel tube chemical composition by weight percentage content is respectively: C 0.07%-0.12%; Si 0.05%-0.25%; Mn 0.90%-1.20%; P 0%-0.015%; S 0%-0.005%; Cr 0.20%-0.50%; Mo 0.10%-0.30%; Nb 0.02%-0.06%; Ti 0.01%-0.03%; Al 0.01%-0.04%; Rare earth elements RE 0.0005%-0.0100%; Cu 0%-0.10%; Surplus is matrix Fe and micro impurity element; Wherein rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
Wherein said containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe, and the component comprising following weight part is prepared from:
Blast-melted: 90 parts;
Steel scrap: 10 parts;
Pre-deoxidation alloy: 1.5-2.3 part;
Ferroaluminium: 0.03-0.12 part;
Lime block: 0.2 part;
Ferro-molybdenum: 0.17-0.50 part;
Ferrocolumbium: 0.03-0.10 part
Ferro-titanium: 0.04-0.12 part;
Rare-earth wires: 0.02 part;
Silicon-calcium wire: 0.06 part;
Wherein said rare-earth wires by rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
Wherein said pre-deoxidation alloy is selected from the mixture of two or more arbitrary proportion in silicomanganese, manganeseirom and ferrochrome.
A kind of production is described containing the resistance to H of rare earth low cost
2s corrodes the method for L320NS seamless steel pipe for line pipe, comprises the steps:
(1) blast-melted pre-treatment: described blast-melted middle S content is reduced to weight percent less than 0.010%;
(2) top and bottom combined blown converter smelting: the blast-melted and described steel scrap after described process is added top and bottom combined blown converter smelting, described pre-deoxidation alloy is adopted to carry out pre-deoxidation alloying in tapping process, final deoxygenation adopts ferroaluminium to carry out there is aluminium deoxidation technique, tapping process carries out pushing off the slag or skims, and adds described lime block after tapping process interalloy adds;
(3) LF stove refining: the molten steel after step (2) being smelted adds the refining of LF stove, blowing argon gas during refining, adopts and counts to the mode heat temperature raising that senior number improves heat-up rate gradually from rudimentary temperature is risen to 1630 DEG C from 1530 DEG C; Employing is made white slag and is operated and add described ferro-molybdenum, described ferrocolumbium and described ferro-titanium; Finally keep bottom soft blow argon gas, add described rare-earth wires;
(4) VD vacuum-treat: vacuum treated vacuum tightness≤0.10KPa, behind dark vacuum time >=13 minute, feeds described silico-calcium silk, carries out >=10 minutes soft blow argon gas after feeding silk;
(5) round billet continuous casting: adopt the fixed speed control of low pulling rate and induction stirring technique and control molten steel overheat≤30 DEG C and carry out round billet continuous casting: strand goes out the laggard row aligning in cooling twice region, is then cut into circular pipe blank;
(6) heating of pipe blank → perforation → tandem rolling → reheat → sizing → aligning → cooling → sawing → flaw detection → chamfered edge is carried out after, the reheating furnace temperature wherein reheated controls between 900 ~ 930 DEG C, finishing temperature control is between 860 ~ 900 DEG C, after sizing, body temperature controls between 830 ~ 880 DEG C, to reach effect of rolling normalizing; Perform band temperature correction straight, straightening temperature >=500 DEG C, carry out scale sawing after then being cooled on cold bed by steel pipe; Then to steel pipe by Zhi Jinhang carrying out flaw detection, eligible carries out chamfered edge processing at two ends.
Wherein said pre-deoxidation alloy is selected from the mixture of two or more arbitrary proportion in silicomanganese, manganeseirom and ferrochrome.
Wherein said rare-earth wires by rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
The invention difference from existing technology is that the present invention achieves following technique effect:
1. owing to being raw material with blast-melted, impurity element Cu content is lower, Cu :≤0.10%;
2. straight owing to carrying out band temperature correction more than 500 DEG C, the unrelieved stress of steel pipe is lower, unrelieved stress :≤30MPa (adopting ring cutting method);
3. because " unique component containing rare earth element designs " is in conjunction with ripe production technique, make the properties of steel pipe excellent, specific performance index is as follows:
Yield strength: 330 ~ 390MPa; Tensile strength: 460 ~ 540MPa; Yield tensile ratio≤0.80; Unit elongation>=30%; Traverse impact value a when 0 DEG C
kV>=100J/cm
2; Shear ratio: 100%; Grain fineness number>=8.0 grade; Hardness≤220HV10; Unrelieved stress≤30MPa.
4. Properties of HIC resistance
According to NACE Standard TM 0284-2003 standard A method, soaking the solution A that sample carries out continuous 96 hours, there is not crackle in specimen surface.
5. anti-SSC performance
According to NACE Standard TM 0177-2005 standard A method, adopt four-point bending SAMPLE METHOD, test constant stress is 0.8
rt0.5(256MPa), through H
2there is not cracking or destructive crackle in the solution A successive soaking that S is saturated, 720 hours samples.
The present invention is directed to Problems existing in background technology, by technical measures such as " unique chemical composition design and be unique production technique of raw material with blast-melted ", solve the problems referred to above well, achieve significant progress.
Embodiment
Below in conjunction with embodiment 1 ~ embodiment, 3 couples of the present invention are described in further detail.
The whole smelting technology of embodiment 1 ~ embodiment 3, rolling technology and thermal treatment process are identical, and difference is alloy addition and chemical composition, and specific implementation process is as follows:
90 tons of blast-melted use 0.03 ton " metal magnesium powder " is done desulfating and deoxidation pre-treatment, makes measuring containing S in molten iron be reduced to (weight percent) less than 0.010%;
Described 90 tons of preprocessed molten irons are blended in the top and bottom combined blown converter of 100 tonnes, add 10 tons of high-quality steel scraps again, then single slag technique is adopted to smelt, in finishing slag, the weight percent of calcium oxide and silicon-dioxide controls by 3.0, adopt silicomanganese, ferromanganese and ferrochrome to carry out deoxidation alloying, the ferroaluminium adopted when tapping carries out final deoxygenation, the necessary pushing off the slag of tapping process, pushing off the slag unsuccessfully must be skimmed, and adds 0.2 ton of lime block after tapping process interalloy adds;
The molten steel smelted is loaded ladle enter furnaceman LF position and carry out refining: normal blowing argon gas (flow be per minute 100 mark rise) on request during refining, adopt and count to the mode heat temperature raising that senior number improves heat-up rate gradually from rudimentary temperature is risen to 1630 DEG C from 1530 DEG C; Slag making desulfurization, composition adjustment and warming temperature is carried out according to converter molten steel composition and temperature; White slag operation is made in employing, adds molybdenum-iron, ferro-niobium and ferro-titanium;
Bottom soft blow argon gas (flow is that per minute 40 marks liter) to be kept after the refining of LF stove terminates, add 0.02 ton of rare-earth wires simultaneously;
Then good to refining molten steel carries out VD vacuum-treat again: dark vacuum tightness≤0.10KPa, dark vacuum time >=13 minute; Feed the silicon-calcium wire (quality is 0.06 ton) of 240 meters again, after feeding silk, keep 12 minutes soft blow argon gas (flow is that per minute 40 marks liter).
Large for molten steel after VD vacuum-treat bag is hung on ladle turret to carry out 5 machines 5 and flow round billet continuous casting, during continuous casting, adopt fixed speed control and the induction stirring technique of low pulling rate; Molten steel overheat Δ T≤30 DEG C; Strand goes out cooling twice region laggard row aligning, is then circular pipe blank with flame cutting.
The concrete alloy addition of embodiment 1 ~ embodiment 3 is in table 1.
Alloy addition (kilogram) in table 1 embodiment 1 ~ embodiment 3
| ? | Silicomanganese | Ferromanganese | Ferrochrome | Molybdenum-iron | Ferro-aluminum | Ferro-niobium | Ferrotianium |
| Embodiment 1 | 850 | 400 | 350 | 400 | 60 | 90 | 50 |
| Embodiment 2 | 700 | 700 | 400 | 350 | 80 | 70 | 60 |
| Embodiment 3 | 600 | 900 | 600 | 300 | 130 | 50 | 70 |
To the specification in embodiment 1 ~ embodiment 3 be
pipe sampling carrying out, inspection, its chemical composition result of laboratory test (weight percent content) is in table 2.
Table 2 chemical composition detected result (% by weight)
Described rare earth elements RE (weight ratio) is: the norium that the La of the Ce+33% of 67% is formed, its chemical composition and content qualified.
Sufur printing: be all no more than 1.0 grades, macroscopic examination is qualified.
The pipe changed, be up to the standards is carried out tubulation, and tubulation process is as follows:
In order to make pipe have good rolling performance, continuous detecting and controlling preheating section, heating zone, the soaking zone temperature of process furnace, ensure that heating is thorough evenly and not overheated, the span of control of each section of temperature is in table 3.
Table 3 rotary heating furnace each section of temperature controls (DEG C)
Carry out automatically controlling and automatic record to process furnace each section of temperature with microcomputer.
Hot tool must be measured before use, must check, processes roller-way before rolling, and avoids scratching tube wall.
The pipe heated is rolled in Ф 159mmPQF continuous rolling-tube unit weldless steel tube (specification is ф 168.3mm × 14.60mm), often criticizes and carry out once heat sampling, check geometrical dimension.
Steel pipe after tandem rolling takes off pipe enters reheating furnace, and reheating furnace temperature controls between 900 ~ 930 DEG C, and finishing temperature control is between 860 ~ 890 DEG C, and after sizing, body temperature controls between 850 ~ 870 DEG C, to reach effect of rolling normalizing.
Steel pipe straightening temperature controls between 520 ~ 530 DEG C, carries out scale sawing after then being cooled on cold bed by steel pipe.
Through above-mentioned explained hereafter and nondestructiving inspecting test, eligible carries out chamfered edge processing at two ends, becomes of the present invention " containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe " finished product.Produce sample with it and carry out mechanical properties test.
Through inspection, embodiment 1 ~ 3 produce line pipe mechanics properties testing value in table 4, SSC performance, HIC performance, tissue, grain fineness number, unrelieved stress assay in table 5.
Table 4 mechanical properties of pipe detected result
Table 5 SSC performance, HIC performance, tissue, grain fineness number, unrelieved stress assay
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (6)
1. one kind contains the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe, it is characterized in that: described weldless steel tube chemical composition by weight percentage content is respectively: C 0.07%-0.12%; Si 0.05%-0.25%; Mn 0.90%-1.20%; P 0%-0.015%; S 0%-0.005%; Cr 0.20%-0.50%; Mo 0.10%-0.30%; Nb 0.02%-0.06%; Ti 0.01%-0.03%; Al 0.01%-0.04%; Rare earth elements RE 0.0005%-0.0100%; Cu 0%-0.10%; Surplus is matrix Fe and micro impurity element; Wherein rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
2. according to claim 1 containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe, it is characterized in that the component that it comprises following weight part is prepared from:
Blast-melted: 90 parts;
Steel scrap: 10 parts;
Pre-deoxidation alloy: 1.5-2.3 part;
Ferroaluminium: 0.03-0.12 part;
Lime block: 0.2 part;
Ferro-molybdenum: 0.17-0.50 part;
Ferrocolumbium: 0.03-0.10 part
Ferro-titanium: 0.04-0.12 part;
Rare-earth wires: 0.02 part;
Silicon-calcium wire: 0.06 part;
Wherein said rare-earth wires by rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
3. according to claim 1 containing the resistance to H of rare earth low cost
2s corrodes L320NS seamless steel pipe for line pipe, it is characterized in that described pre-deoxidation alloy is selected from the mixture of two or more arbitrary proportion in silicomanganese, manganeseirom and ferrochrome.
4. produce according to any one of claim 1-3 containing the resistance to H of rare earth low cost for one kind
2s corrodes the method for L320NS seamless steel pipe for line pipe, it is characterized in that comprising the steps:
(1) blast-melted pre-treatment: described blast-melted middle S content is reduced to weight percent less than 0.010%;
(2) top and bottom combined blown converter smelting: the blast-melted and described steel scrap after described process is added top and bottom combined blown converter smelting, described pre-deoxidation alloy is adopted to carry out pre-deoxidation alloying in tapping process, final deoxygenation adopts ferroaluminium to carry out there is aluminium deoxidation technique, tapping process carries out pushing off the slag or skims, and adds described lime block after tapping process interalloy adds;
(3) LF stove refining: the molten steel after step (2) being smelted adds the refining of LF stove, blowing argon gas during refining, adopts and counts to the mode heat temperature raising that senior number improves heat-up rate gradually from rudimentary temperature is risen to 1630 DEG C from 1530 DEG C; Employing is made white slag and is operated and add described ferro-molybdenum, described ferrocolumbium and described ferro-titanium; Finally keep bottom soft blow argon gas, add described rare-earth wires;
(4) VD vacuum-treat: vacuum treated vacuum tightness≤0.10KPa, behind dark vacuum time >=13 minute, feeds described silico-calcium silk, carries out >=10 minutes soft blow argon gas after feeding silk;
(5) round billet continuous casting: adopt the fixed speed control of low pulling rate and induction stirring technique and control molten steel overheat≤30 DEG C and carry out round billet continuous casting: strand goes out the laggard row aligning in cooling twice region, is then cut into circular pipe blank;
(6) heating of pipe blank → perforation → tandem rolling → reheat → sizing → aligning → cooling → sawing → flaw detection → chamfered edge is carried out after, the reheating furnace temperature wherein reheated controls between 900 ~ 930 DEG C, finishing temperature control is between 860 ~ 900 DEG C, after sizing, body temperature controls between 830 ~ 880 DEG C, to reach effect of rolling normalizing; Perform band temperature correction straight, straightening temperature >=500 DEG C, carry out scale sawing after then being cooled on cold bed by steel pipe; Then to steel pipe by Zhi Jinhang carrying out flaw detection, eligible carries out chamfered edge processing at two ends.
5. according to claim 4 containing the resistance to H of rare earth low cost
2s corrodes the production method of L320NS seamless steel pipe for line pipe, it is characterized in that: described pre-deoxidation alloy is selected from the mixture of two or more arbitrary proportion in silicomanganese, manganeseirom and ferrochrome.
6. according to claim 4 containing the resistance to H of rare earth low cost
2s corrodes the production method of L320NS seamless steel pipe for line pipe, it is characterized in that: described rare-earth wires by rare earth elements RE component is: the Ce of the 67% and La of 33% makes.
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| CN201410620607.XA CN104313474A (en) | 2014-11-06 | 2014-11-06 | Seamless steel tube for rare earth containing low-cost H2S corrosion-resistant L320NS pipeline and production method thereof |
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Cited By (5)
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| CN107338399A (en) * | 2017-06-28 | 2017-11-10 | 包头钢铁（集团）有限责任公司 | Shale gas seamless pipe of high tenacity containing rare earth high-strength and preparation method thereof |
| CN107619994A (en) * | 2017-04-27 | 2018-01-23 | 中国石油大学(北京) | A kind of anti-CO2/H2S and sulfate reducing bacteria corrosion seamless line pipe and its manufacture method |
| CN109023093A (en) * | 2018-09-10 | 2018-12-18 | 台山永发五金制品有限公司 | A kind of high strength steel and preparation method thereof |
| CN110983156A (en) * | 2019-11-27 | 2020-04-10 | 上海大学 | Rare earth corrosion-resistant steel rich in alloying rare earth elements and manufacturing method thereof |
| CN111155027A (en) * | 2019-12-26 | 2020-05-15 | 包头钢铁（集团）有限责任公司 | Low-alloy high-strength seamless steel tube for rare earth-containing Q390 structure and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619994A (en) * | 2017-04-27 | 2018-01-23 | 中国石油大学(北京) | A kind of anti-CO2/H2S and sulfate reducing bacteria corrosion seamless line pipe and its manufacture method |
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| CN110983156A (en) * | 2019-11-27 | 2020-04-10 | 上海大学 | Rare earth corrosion-resistant steel rich in alloying rare earth elements and manufacturing method thereof |
| CN111155027A (en) * | 2019-12-26 | 2020-05-15 | 包头钢铁（集团）有限责任公司 | Low-alloy high-strength seamless steel tube for rare earth-containing Q390 structure and preparation method thereof |
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