CN103667929A - Low-cost and H2S-corrosion-resistant L390NS pipeline tube containing rare earth and production method of pipeline tube - Google Patents
Low-cost and H2S-corrosion-resistant L390NS pipeline tube containing rare earth and production method of pipeline tube Download PDFInfo
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- CN103667929A CN103667929A CN201310616341.7A CN201310616341A CN103667929A CN 103667929 A CN103667929 A CN 103667929A CN 201310616341 A CN201310616341 A CN 201310616341A CN 103667929 A CN103667929 A CN 103667929A
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Abstract
The invention provides a low-cost and H2S-corrosion-resistant L390NS pipeline tube containing rare earth and a production method of the pipeline tube, and belongs to the technical field of metallurgy and molding. A tube blank comprises chemical components as follows: 0.07wt%-0.12wt% of C, 0.05wt%-0.25wt% of Si, 1.00wt%-1.30wt% of Mn, smaller than or equal to 0.015wt% of P, smaller than or equal to 0.005wt% of S, 0.50wt%-0.80wt% of Cr, 0.10wt%-0.30wt% of Mo, 0.02wt%-0.06wt% of Nb, 0.01wt%-0.03wt% of Ti, 0.01wt%-0.04wt% of Al, 0.0005wt%-0.0100wt% of RE and smaller than 0.10% of Cu; the technological processes are as follows: molten iron pretreatment, converter smelting, refinement, vacuum treatment, continuous casting, cutting, tube blank heating, punching, continuous rolling, reheating, sizing, straightening, cooling, saw cutting, flaw detection and chamfering; and the yield strength is 400-460 MPa, and the transverse impact value is larger than or equal to 80 J/cm<2> at the temperature of 0 DEG C. The low-cost and H2S-corrision-resistant L390NS pipeline tube containing rare earth has the characteristics of low production cost, high toughness matching performance, small crystal particle and high H2S corrosion resistance.
Description
One, affiliated technical field:
The invention belongs to ferrous metal smelting and stress metal manufacture field, relate to a kind of containing the low-cost resistance to H of rare earth
2s corrosion L390NS seamless steel pipe for line pipe and production method thereof.
Two, 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 transportation of pipeline, need high grade of 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 two kinds of collapse modes of hydrogen induced cracking (HIC) (HIC).These two kinds of collapse modes all produced serious accident in Oil and Natural Gas Transportation Pipeline.For this reason, in succession developed moisture-resistant H both at home and abroad
2s corroded pipeline pipe, the application of these materials has effectively prevented 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: CN1351189A), it exists following problem and shortcoming:
Impurity element Cu (% by weight≤0.20%) content is high.This is to take the deficiency that steel scrap cannot overcome by electric furnace production technique as raw material, because the fusing point of Cu element is low, this can give smelt, the operation of rolling cause certain difficulty.
Three, 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
2s stress corrosion raw can be high containing the low-cost seamless steel pipe for line pipe of rare earth and production method thereof.
The object of the present invention is achieved like this:
Using the high-quality steel scrap of the blast-melted of weight percent 90% and 10% as raw material.
With following technical process, produce: first to the above-mentioned blast-melted pre-treatment of carrying out, then together add top and bottom combined blown converter to smelt with above-mentioned high-quality steel scrap, the molten steel of having smelted being packed into ladle enters furnaceman LF position and carries out refining again, after refining completes, enter VD station and carry out Fruit storage, carry out again round billet continuous casting, and continuously cast bloom is cut into pipe, then continuously cast billet for pipe-making is heated, the pipe heating is bored a hole and become Continuous Seamless Tube Mill with tandem rolling, tube rolling is reheated to temperature raising, through after sizing, align, then send into cold bed cooling, implement afterwards sawing, finally by carrying out flaw detection, eligible is line pipe finished product after chamfered edge processing.
Its brief description of the process is: hot metal pretreatment → top and bottom combined blown converter smelting → LF stove refining → VD vacuum-treat → round billet continuous casting → cutting → heating of pipe blank → perforation → tandem rolling → reheat → sizing → aligning → cooling → sawing → flaw detection → chamfered edge.
The production process of continuous casting circular tube blank is as described below:
1, by blast-melted through pre-treatment, make being reduced to below 0.010% containing S amount (weight percent) in molten iron.
2, pretreated molten iron is blended into top and bottom combined blown converter, add (weight percent) 10% high-quality steel scrap, adopt single slag technique to smelt, control finishing slag basicity and terminal target, in tapping process, carry out deoxidation alloying, final deoxygenation adopts aluminium deoxidation technique, and tapping process must pushing off the slag or skimmed, and after tapping process interalloy adds, adds lime piece.
3, at LF stove, carry out concise: refining whole process is normally blown Ar on request, adopt from rudimentary and count to the mode that senior number improves heat-up rate gradually and heat temperature raising; According to converter molten steel composition and temperature, carry out slag making desulfurization, composition adjustment and warming temperature; White slag operation is made in employing.
4, the refining of LF stove finishes rear maintenance bottom soft blow Ar, by predetermined add-on feeding rare-earth wires.
5, carry out VD vacuum-treat: vacuum tightness≤0.10KPa, dark vacuum time >=13 minute.
6, feeding fixed length silico-calcium silk, carries out blowing for 8～10 minutes Ar after hello silk; Molten steel after VD vacuum-treat is carried out to round billet continuous casting, adopt the constant speed of low pulling rate to control and induction stirring technique; Control molten steel overheat; Strand is after aligning, and flame cutting is circular pipe blank.
Pipe is carried out to chemical composition chemical examination, and the chemical composition of pipe should meet following requirement (weight percent %): C0.07～0.12; Si0.05～0.25; Mn1.00～1.30; P≤0.015; S≤0.005; Cr0.50～0.80; Mo0.10～0.30; Nb0.02～0.06; Ti0.01～0.03; Al0.01～0.04; Rare earth elements RE 0.0005～0.010; Cu<0.10; Surplus is matrix Fe and the micro impurity element that cannot detect.
Described rare earth elements RE is the norium of Ce, La, and their weight percent is respectively: Ce67%, La33%.
Add rare earth element to play and improve the effects such as non-metallic inclusion form, strengthening crystal boundary, thereby obtain the effect that improves corrosion resistance nature and impelling strength.
Composition is chemically examined to the continuous casting circular tube blank that qualified and sufur printing is not more than 2.0 grades and carry out tubulation, tubulation process is as follows:
Pipe is put into process furnace and heat, continuous review the temperature of each sections such as process furnace preheating section, heating zone, soaking zone controlled well, the span of control of each section of temperature is in Table 1;
Each section of temperature control of table 1 rotary heating furnace (℃)
| Pipe specification | Preheated one-section | Two sections of preheatings | Heat one section | Heat two sections | One section of soaking | Two sections of soaking |
| Φ180mm | -- | -- | -- | 1260～1300 | 1260～1300 | 1260～1300 |
| Φ270mm | 1050～1120 | 1150～1250 | 1250～1290 | 1270～1310 | 1270～1300 | 1260～1300 |
With microcomputer, each section of temperature of process furnace carried out automatically controlling and automatic record.
Hot tool must be measured before use, rolls front necessary inspection, processes roller-way, avoids scratching tube wall.
The pipe heating is rolled into respectively to the weldless steel tube of required specification in corresponding continuous rolling-tube unit, during rolling, every batch is at least carried out once heat sampling, checks geometrical dimension;
Steel pipe after the de-pipe of tandem rolling enters reheating furnace, and reheating furnace temperature is controlled between 900～930 ℃, and finishing temperature is controlled between 860～900 ℃, and after sizing, body temperature is controlled between 830～880 ℃, to reach the effect of rolling normalizing;
Carry out band temperature correction straight, straightening temperature >=500 ℃, carry out scale sawing after then steel pipe is cooling on cold bed.
Then to steel pipe by Zhi Jinhang carrying out flaw detection, eligible carries out chamfered edge processing at two ends.
Through above-mentioned technological process, can produce of the present invention " containing the low-cost resistance to H of rare earth
2s corrosion L390NS seamless steel pipe for line pipe ".
The beneficial effect of the invention:
1. owing to take blast-melted, be raw material, impurity element Cu content is lower, Cu≤0.10%;
2. owing to being with above temperature correction straight at 500 ℃, the unrelieved stress of steel pipe is lower, unrelieved stress≤30MPa (adopting ring cutting method);
3. because " containing the unique component design of rare earth element " is in conjunction with ripe production technique, make the properties of steel pipe excellent, concrete life can refer to as follows:
Yield strength: 400～460MPa; Tensile strength: 550～620MPa; Yield tensile ratio≤0.80; Unit elongation>=29%; Traverse impact value a in the time of 0 ℃
kV>=80J/cm
2; Shear ratio: 100%; Grain fineness number>=8.0 grade; Hardness≤225HV10; Unrelieved stress≤30MPa.
4. Properties of HIC resistance
According to NACE Standard TM0284-2003 standard A method, sample is carried out to the A solution soaking of continuous 96 hours, there is not crackle in specimen surface.
5. anti-SSC performance
According to NACE Standard TM01772005 standard A method, adopt four-point bending SAMPLE METHOD, test constant stress is 0.8R
t0.5(312MPa), through H
2there is not cracking in the A solution successive soaking that S is saturated, 720 hours samples.
The present invention is directed to the problem existing in background technology, by technical measures such as " unique chemical composition design and the blast-melted unique production technique as raw material of take ", solved well the problems referred to above, obtained significant progress.
Four, embodiment:
Below in conjunction with 3 couples of the present invention of embodiment 1～embodiment, be described in further detail.
By weight raw material be: blast-melted 90%, high-quality steel scrap 10%.
The technological process of production is sequentially: hot metal pretreatment → top and bottom combined blown converter smelting → LF stove refining → VD vacuum-treat → round billet continuous casting → cutting → heating of pipe blank → perforation → tandem rolling → reheat → sizing → aligning → cooling → sawing → flaw detection → chamfered edge.
The concrete technological process of production is summarized as follows:
90 tons of blast-melted use " metal magnesium powder " are done to desulfating and deoxidation pre-treatment, make measuring and being reduced to (weight percent) below 0.010% containing S in molten iron;
90 tons of described preprocessed molten irons are blended in the top and bottom combined blown converter of 100 tonnes, add again 10 tons of high-quality steel scraps, then adopt single slag technique to smelt, finishing slag basicity is controlled by 3.0, during tapping, adopt silicomanganese, ferromanganese and ferrochrome to carry out deoxidation alloying, final deoxygenation adopts aluminium deoxidation technique, the necessary pushing off the slag of tapping process, pushing off the slag unsuccessfully must be skimmed, and adds 200kg lime piece after tapping process interalloy adds.
Packing the molten steel of having smelted into ladle enters furnaceman LF position and carries out refining: normal Argon on request during refining, adopts from rudimentary and count to the mode heat temperature raising that senior number improves heat-up rate gradually; According to converter molten steel composition and temperature, carry out slag making desulfurization, composition adjustment and warming temperature; White slag operation is made in employing, and molybdenum-iron, ferro-niobium and ferro-titanium added in the middle and later periods;
After finishing, the refining of LF stove to keep bottom soft blow Ar, by the rare-earth wires of predetermined add-on feeding certain length.
Then the good molten steel of refining is carried out to VD vacuum-treat again: dark vacuum tightness≤0.10KPa, dark vacuum time >=13 minute; Feed again the silicon-calcium wire of certain length, feed silk rear 8～10 minutes soft blow Ar of maintenance.
The large bag of molten steel after VD vacuum-treat is hung on to ladle turret and carry out 5 machine 5 stream round billet continuous castings, during continuous casting, adopt the constant speed of low pulling rate to control and induction stirring technique; Molten steel overheat Δ T≤30 ℃; Strand is aligned after going out territory, secondary cooling zone, with flame cutting, is then circular pipe blank.
To pipe samplingization, check, 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 67% Ce+33% forms, its chemical composition and content thereof are qualified.
Sufur printing: be all no more than 1.0 grades, macroscopic examination is qualified.
The pipe of changing, being up to the standards is carried out to tubulation, and tubulation process is as follows:
In order to make pipe there is good rolling performance, continuous detecting and control preheating section, heating zone, the soaking zone temperature of process furnace, guarantee that heating is thoroughly evenly and not overheated, the span of control of each section of temperature is in Table 1.
With microcomputer, each section of temperature of process furnace carried out automatically controlling and automatic record.
Hot tool must be measured before use, rolls front necessary inspection, processes roller-way, avoids scratching tube wall.
The pipe heating is rolled into the weldless steel tube that specification is ф 168.3m * 14.60m in Φ 159mlalPQF continuous rolling-tube unit, and every batch is carried out once heat sampling, checks geometrical dimension; Steel pipe after tandem rolling enters reheating furnace, and reheating furnace temperature is controlled between 900～930 ℃, and after sizing, body temperature is controlled between 850～880 ℃.
Steel pipe straightening temperature is controlled between 520～530 ℃, carries out scale sawing after then steel pipe is cooling on cold bed;
Through E, state explained hereafter and nondestructiving inspecting test, eligible carries out chamfered edge processing at two ends, becomes of the present invention " containing the low-cost resistance to H of rare earth
2s corrosion L390NS seamless steel pipe for line pipe " finished product.With it, produce sample and carry out mechanical properties test.
Through check, the mechanical property detected value of embodiment 1～3 seamless steel pipe for line pipe that produces in Table 3, HTC performance, SSC performance, tissue, grain fineness number, unrelieved stress assay be in Table 4.
Table 3 mechanical properties of pipe detected result
Table 4 HTC performance, SSC performance, tissue, grain fineness number, unrelieved stress assay
| ? | HIC performance | SSC performance (sample fracture time) | Tissue | Grain fineness number | Unrelieved stress |
| Embodiment 1 | CSR=0，CLR=0，CTR=0 | Constant stress 31ZVlPa, >=720 hours | F+P | 9.0 level | 17MPa |
| Embodiment 2 | CSR=0，CLR=0，CTR=0 | Constant stress 31ZVlPa, >=720 hours | F+P | 9.0 level | 19MPa |
| Embodiment 3 | CSR=0，CLR=0，CTR=0 | Constant stress 31ZVlPa, >=720 hours | F+P | 9.0 level | 20MPa |
Claims (10)
1. one kind contains the low-cost resistance to H of rare earth
2s corrosion L390NS line pipe, is characterized in that the high-quality steel scrap blast-melted and 10% that raw material is 90% by weight percent forms, and its chemical composition is respectively by weight percentage: C0.07～0.12; Si0.05～0.25; Mn1.00～1.30; P≤0.015; S≤0.005; Cr0.50～0.80; Mo0.10～0.30; Nb0.02～0.06; Ti0.01～0.03; Al0.01～0.04; Rare earth elements RE 0.0005～0.0100; Cu<0.10, surplus is matrix Fe and the micro impurity element that cannot detect; The mechanical property of product: yield strength 400～460MPa, unrelieved stress≤30MPa, the traverse impact value a 0 ℃ time
kV>=80J/cm
2, grain fineness number>=8.0 grade; SSC performance: constant stress is 0.8Rt
0.5=312MPa, through H
2a solution successive soaking, 720 hours samples that S is saturated do not rupture; HIC performance: CSR=0, CLR=0, CTR=0.
2. according to claim 1 a kind of containing the low-cost resistance to H of rare earth
2s corrosion L390NS line pipe, is characterized in that RE is the norium of Ce and La, and its weight percent is: Ce67%, La33%.
3. feature a kind of containing the low-cost resistance to H of rare earth as claimed in claim 1
2the production method of S corrosion L390NS line pipe, is characterized in that technological process of production summary is: hot metal pretreatment → top and bottom combined blown converter smelting → LF stove refining → VD vacuum-treat → round billet continuous casting → cutting → heating of pipe blank → perforation → tandem rolling → reheat → sizing → aligning → cooling → sawing → flaw detection → chamfered edge.
4. according to claim 3 a kind of containing the low-cost resistance to H of rare earth
2the production method of S corrosion L390NS line pipe, is characterized in that blast-melted, through pre-treatment, making S content in molten iron be reduced to weight percent below 0.010%; Pretreated molten iron and high-quality steel scrap are added to top and bottom combined blown converter by design proportion respectively, adopt single slag technique to smelt, control finishing slag basicity and terminal target; In tapping process, carry out deoxidation alloying, final deoxygenation adopts aluminium deoxidation technique, and tapping process must pushing off the slag or skimmed, and after tapping process interalloy adds, adds lime piece.
5. according to claim 3 a kind of containing the low-cost resistance to H of rare earth
2the production method of S corrosion L390NS line pipe, is characterized in that carrying out concise at LF stove; Refining whole process is normal Argon on request, adopts from rudimentary and counts to the mode heat temperature raising that senior number improves heat-up rate gradually; According to converter molten steel composition and temperature, carry out slag making desulfurization, composition adjustment and warming temperature; White slag operation is made in employing.
6. according to a kind of low-cost resistance to H of rare earth that contains described in claim 3 or 5
2the production method of S corrosion L390NS line pipe, is characterized in that the refining of LF stove finishes rear maintenance bottom soft blow Ar, by predetermined add-on feeding rare-earth wires.
7. according to claim 3 a kind of containing the low-cost resistance to H of rare earth
2the production method of S corrosion L390NS line pipe, is characterized in that carrying out the vacuum treated vacuum tightness≤0.10KPa of VD, dark vacuum time>=13 minute.
8. according to a kind of low-cost resistance to H of rare earth that contains described in claim 3 or 7
2the production method of S corrosion L390NS line pipe, feeds fixed length silico-calcium silk while it is characterized in that VD vacuum-treat, after hello silk, carry out blowing for 8～10 minutes Ar.
9. according to claim 3 a kind of containing the low-cost resistance to H of rare earth
2the production method of S corrosion L390NS line pipe, while it is characterized in that carrying out round billet continuous casting, adopts constant speed control and the induction stirring technique of low pulling rate and controls molten steel overheat≤30 ℃; Strand is aligned after going out territory, secondary cooling zone, is then cut into circular pipe blank.
10. according to claim 3 a kind of containing the low-cost resistance to H of rare earth
2the production method of S corrosion L390NS line pipe, it is characterized in that adopting non-modifier treatment technique, reheating furnace temperature is controlled at 900～930 ℃, and finishing temperature is controlled at 860～900 ℃, after sizing, body temperature is controlled at 830～880 ℃, to reach the effect of rolling normalizing.
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Cited By (4)
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| CN104313474A (en) * | 2014-11-06 | 2015-01-28 | 内蒙古包钢钢联股份有限公司 | Seamless steel tube for rare earth containing low-cost H2S corrosion-resistant L320NS pipeline and production method thereof |
| CN104532138A (en) * | 2015-01-06 | 2015-04-22 | 内蒙古包钢钢联股份有限公司 | Seamless steel tube containing rare earth for L360NO subsea pipeline and production method thereof |
| CN111118399A (en) * | 2020-02-20 | 2020-05-08 | 包头钢铁（集团）有限责任公司 | Corrosion-resistant high-crack-resistance submarine pipeline steel X65MO with thickness of 15-22mm and production method thereof |
| CN111235465A (en) * | 2020-02-20 | 2020-06-05 | 包头钢铁（集团）有限责任公司 | Corrosion-resistant high-crack-resistance submarine pipeline steel X65MO with thickness of 8-15mm and production method thereof |
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| CN104532138A (en) * | 2015-01-06 | 2015-04-22 | 内蒙古包钢钢联股份有限公司 | Seamless steel tube containing rare earth for L360NO subsea pipeline and production method thereof |
| CN111118399A (en) * | 2020-02-20 | 2020-05-08 | 包头钢铁（集团）有限责任公司 | Corrosion-resistant high-crack-resistance submarine pipeline steel X65MO with thickness of 15-22mm and production method thereof |
| CN111235465A (en) * | 2020-02-20 | 2020-06-05 | 包头钢铁（集团）有限责任公司 | Corrosion-resistant high-crack-resistance submarine pipeline steel X65MO with thickness of 8-15mm and production method thereof |
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