CN103215518B - Containing the resistance to H of rare earth 2the preparation method of S corroded pipeline weldless steel tube - Google Patents
Containing the resistance to H of rare earth 2the preparation method of S corroded pipeline weldless steel tube Download PDFInfo
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Abstract
The invention discloses a kind of containing the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube, comprise: the production process of continuous casting circular tube blank and tubulation process, the production process of continuous casting circular tube blank comprises: hot metal pretreatment, top and bottom combined blown converter smelting, the refining of LF stove, VD vacuum-treat, round billet continuous casting and cutting; Tubulation process comprises: heating of pipe blank, perforation, tandem rolling, reheat, sizing or tube reducing, aligning, cooling, sawing, flaw detection and chamfered edge.The resistance to H of weldless steel tube prepared by the present invention
2s stress corrosion performance is higher.
Description
Technical field
The present invention relates to ferrous metal smelting and metal-pressed machine field, specifically, relate to a kind of containing the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube.
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 Destroy type.These two kinds of Destroy type 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 corrodes L290NS Hi-grade steel line pipe, and the application of these materials effectively prevents generation and the destruction of Wet hydrogen sulfide corrosion.
Chinese invention patent CN1351189A discloses a kind of Ultra-low carbon high tenacity anti-H 2 S steel for gas delivering pipeline, but impurity element Cu (wt%≤0.20%) content is high.This is the deficiency that the technique of producing for raw material electric furnace with steel scrap cannot overcome, and because the fusing point of Cu element is low, this can give smelting, the operation of rolling causes certain difficulty.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of containing the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube, can prepare resistance to H
2the weldless steel tube that S stress corrosion performance is high, weldless steel tube has excellent performance simultaneously.
Technical scheme of the present invention is as follows:
A kind of containing the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube, comprising: the production process of continuous casting circular tube blank and tubulation process; What prepare is described containing the resistance to H of rare earth
2the mass percentage of the chemical composition of S corroded pipeline weldless steel tube is: C0.06 ~ 0.12, Si0.05 ~ 0.30, Mn0.80 ~ 1.10, Cr0.10 ~ 0.30, Mo0.10 ~ 0.20, V0.03 ~ 0.10, Ti0.01 ~ 0.03, Al0.01 ~ 0.04, rare earth elements RE 0.0005 ~ 0.0100, Cu≤0.10, P≤0.015, S≤0.005, surplus is matrix Fe and impurity element, wherein, described rare earth elements RE comprise mass percentage be 67% Ce and mass percentage be the La of 33%; The production process of described continuous casting circular tube blank comprises: hot metal pretreatment, top and bottom combined blown converter smelting, LF stove (LadleFurnace) refining, VD (VacuumDegassing) vacuum-treat, round billet continuous casting and cutting; Described hot metal pretreatment comprises: molten iron is done desulfating and deoxidation pre-treatment, makes mass percentage≤0.010% of the S in the molten iron after hot metal pretreatment; Described top and bottom combined blown converter smelting comprises: by after described hot metal pretreatment molten iron be blended into top and bottom combined blown converter, add steel scrap, after described hot metal pretreatment molten iron and the mass ratio of described steel scrap be 9:1, single slag technique is adopted to smelt, controlling finishing slag basicity is 3.0, in tapping process, silicomanganese, ferromanganese and ferrochrome carry out deoxidation alloying, wherein, in every 100 tons of tapping molten steel, ferrosilicon is 260kg, ferromanganese is 1200kg, ferrochrome is 200kg, final deoxygenation adopts aluminium deoxidation technique, tapping process pushing off the slag or skim, described tapping molten steel water adds lime block 200kg; The refining of described LF stove comprises: whole process blows Ar, adopts the mode improving heat-up rate gradually to heat temperature raising; Carry out making white slag desulfurization, composition adjustment and warming temperature according to the molten steel composition of described top and bottom combined blown converter smelting and temperature; Ferro-molybdenum 150kg, ferro-vanadium 100kg and ferro-titanium 100kg is added in the middle and later periods of LF stove refining every 100 tons of LF refined molten steel; The refining of described LF stove terminates rear maintenance bottom soft blow Ar, and feed 200 meters of rare-earth wires by predetermined add-on, described predetermined add-on is 0.02% of the quality of LF refined molten steel; Vacuum treated vacuum tightness≤the 0.10KPa of described VD, dark vacuum time>=13 minute, feeding fixed length silico-calcium silk, feeds silk after-blow Ar8 ~ 10 minute; Described round billet continuous casting and cutting comprise: the molten steel after VD vacuum-treat is carried out round billet continuous casting, adopt pulling rate fixed speed control and the induction stirring technique of 1.1m/min; Control molten steel overheat≤30 DEG C; After strand goes out the laggard row aligning in cooling twice region, then flame cutting is circular pipe blank; Described tubulation process comprises: heating of pipe blank, perforation, tandem rolling, reheat, sizing or tube reducing, aligning, cooling, sawing, flaw detection and chamfered edge; Described heating of pipe blank comprises: pipe is put into process furnace and heats, when the diameter of pipe is 180mm, heat two sections be 1260 ~ 1300 DEG C, soaking one section is 1260 ~ 1300 DEG C, soaking two sections is 1260 ~ 1300 DEG C; When the diameter of pipe is 270mm, preheated one-section is 1050 ~ 1120 DEG C, preheating two sections is 1150 ~ 1250 DEG C, heating one section is 1250 ~ 1290 DEG C, heating two sections is 1270 ~ 1300 DEG C, soaking one section is 1270 ~ 1300 DEG C, soaking two sections is 1270 ~ 1300 DEG C; Described reheating comprises: the steel pipe after described tandem rolling enters reheating furnace, and reheating furnace temperature is 900 ~ 930 DEG C, and finishing temperature is 860 ~ 900 DEG C, and after sizing or tube reducing, body temperature is 830 ~ 880 DEG C; Described aligning is that band temperature correction is straight, described band temperature straightening temperature>=500 DEG C.
Further, what prepare is described containing the resistance to H of rare earth
2the mass percentage of the chemical composition of S corroded pipeline weldless steel tube is: C0.09, Si0.19, Mn0.95, Cr0.27, Mo0.13, V0.06, Ti0.017, Al0.025, RE0.0013, Cu0.007, P0.012, S0.003; Or, C0.10, Si0.21, Mn0.97, Cr0.25, Mo0.14, V0.05, Ti0.015, Al0.032, RE0.0012, Cu0.008, P0.013, S0.003; Or, C0.06, Si0.05, Mn1.10, Cr0.30, Mo0.20, V0.10, Ti0.01, Al0.04, RE0.01, Cu0.1, P0.015, S0.005; Or, C0.12, Si0.30, Mn0.80, Cr0.10, Mo0.10, V0.03, Ti0.03, Al0.01, RE0.0005, Cu0.1, P0.009, S0.002.
Technique effect of the present invention is as follows:
1, the present invention is raw material with blast-melted, and impurity element Cu content is lower, mass percentage≤0.10% of Cu.
2, the present invention carries out band temperature correction directly more than 500 DEG C, and the unrelieved stress of steel pipe is lower, and ring cutting method measures unrelieved stress≤25MPa.
3, steel pipe of the present invention contains the rare earth element of unique component, makes steel pipe have excellent performance: yield strength is 320 ~ 380MPa, tensile strength is 450 ~ 520MPa, yield tensile ratio≤0.80, unit elongation>=32%, traverse impact value are a
kV>=160J/cm (0 DEG C), shear than be 100%, hardness≤220HV10, grain fineness number>=8.5 grade.
4, the anti-HIS excellent performance of steel pipe of the present invention, according to U.S. antiseptic project association criterion (NACEStandardTM) 0284-2003 standard A method, soaking the solution A that sample carries out continuous 96 hours, there is not crackle in specimen surface.
5, the anti-SCC excellent performance of steel pipe of the present invention, according to U.S. antiseptic project association criterion (NACEStandardTM) 0177-2005 standard A method, adopts smooth tension specimen method, and test constant stress is 0.8
rt0.5(232MPa), through H
2s saturated solution (solution A) soaks, and within continuous 720 hours, cracking does not appear in sample.
Embodiment
It is raw material with high-quality steel scrap that the present invention adopts blast-melted.Blast-melted mass percentage is 90%, and the mass percentage of high-quality steel scrap is 10%.Preparation method of the present invention comprises: the production process of continuous casting circular tube blank and tubulation process.Concrete production process is as follows:
The production process of continuous casting circular tube blank comprises: hot metal pretreatment → top and bottom combined blown converter smelting → LF stove refining → VD vacuum-treat → round billet continuous casting → cutting
Step S1: hot metal pretreatment
90 tons of blast-melted use " metal magnesium powder " are done desulfating and deoxidation pre-treatment, makes mass percentage≤0.010% of the S in the molten iron after hot metal pretreatment.
Step S2: top and bottom combined blown converter smelting
Molten iron after 90 tons of hot metal pretreatment is 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, it is 3.0 that finishing slag basicity controls, ferrosilicon, ferromanganese, ferrochrome is adopted to carry out deoxidation alloying during tapping, wherein add ferrosilicon 260kg, ferromanganese 1200kg, ferrochrome 200kg, final deoxygenation adopts aluminium deoxidation technique, and tapping process must pushing off the slag.If pushing off the slag failure, must skim, add 200kg lime block in tapping process after adding above-mentioned alloy.
The refining of step S3:LF stove
The molten steel smelted loading ladle is entered furnaceman LF position and carries out refining.Normal Argon on request during refining, adopts the mode heat temperature raising from improving heat-up rate gradually.Slag making desulfurization, composition adjustment and warming temperature is carried out according to converter molten steel composition and temperature.White slag operation desulfurization is made in employing.Molybdenum-iron, vanadium iron and ferro-titanium added in the middle and later periods of LF stove refining, wherein ferro-molybdenum 150kg, ferro-vanadium 100kg, ferro-titanium 100kg.Will keep soft blow Ar in bottom after the refining of LF stove terminates, feed 200 meters of rare-earth wires by predetermined add-on, predetermined add-on is 0.02% of the quality of LF refined molten steel.
Step S4:VD vacuum-treat
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 of 280 meters again, after feeding silk, keep 8 ~ 10 minutes soft blow Ar.
Step S5: round billet continuous casting and cutting
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.Pulling rate fixed speed control and the induction stirring technique of 1.1m/min is adopted during continuous casting.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.
Tubulation process comprises: heating of pipe blank → perforation → tandem rolling → reheat → sizing or tube reducing → aligning → cooling → sawing → flaw detection → chamfered edge.
After testing, the chemical composition of each embodiment is as shown in table 1.
The each embodiment composition of table 1 (mass percent/%)
| Embodiment | C | Si | Mn | Cr | Mo | V | Ti | Al | RE | Cu | P | S |
| 1 | 0.09 | 0.19 | 0.95 | 0.27 | 0.13 | 0.06 | 0.017 | 0.025 | 0.0013 | 0.007 | 0.012 | 0.003 |
| 2 | 0.10 | 0.21 | 0.97 | 0.25 | 0.14 | 0.05 | 0.015 | 0.032 | 0.0012 | 0.008 | 0.013 | 0.003 |
| 3 | 0.06 | 0.05 | 1.10 | 0.30 | 0.20 | 0.10 | 0.01 | 0.04 | 0.01 | 0.10 | 0.015 | 0.005 |
| 4 | 0.12 | 0.30 | 0.80 | 0.10 | 0.10 | 0.03 | 0.03 | 0.01 | 0.0005 | 0.10 | 0.009 | 0.002 |
The micro impurity element that surplus is matrix Fe and cannot detects.Wherein, rare earth elements RE be by mass percentage be 67% Ce and mass percentage be 33% the norium that forms of La.Add rare earth element can play and improve non-metallic inclusion form, effect such as strengthening crystal boundary etc., thus obtain the effect improving corrosion resistance nature and impelling strength.As shown in Table 1, the chemical composition of above-described embodiment and content qualified.Detected by sufur printing, be all no more than 2.0 grades.By macroscopic examination, up-to-standard.
Step S6: heating of pipe blank
In order to make pipe have good rolling performance, pipe being put into process furnace and heats, continuous detecting and control preheating section, heating zone, the soaking zone temperature of process furnace, ensure that heating is thorough evenly and not overheated.Carry out automatically controlling and automatic record to process furnace each section of temperature with microcomputer.The specification of pipe has two kinds, and a kind of pipe specification is Ф 180mm, and another kind of pipe specification is Ф 270mm.The span of control of each section of temperature of two kinds of pipe specifications is in table 2.The pipe specification of embodiments of the invention 1 ~ 4 is Ф 180mm.
Table 2 rotary heating furnace each section of temperature controls (DEG C)
| Pipe specification | Preheated one-section | Preheating two sections | Heat one section | Heat two sections | Soaking one section | Soaking two sections |
| Ф180mm | -- | -- | -- | 1260～1300 | 1260～1300 | 1260～1300 |
| Ф270mm | 1050～1120 | 1050～1250 | 1250～1290 | 1270～1310 | 1270～1300 | 1270～1310 |
Step S7: perforation and tandem rolling
The hot tool of perforation unit must be measured before use, must check, processes roller-way before rolling, and avoids scratching tube wall.The pipe heated is rolled into respectively the weldless steel tube of ф 168.3mm × 14.60mm specification at Ф 159mm tri-roller MPM tube rolling mill (PremiumQualityFinishing, PQF).Often criticize during rolling and at least carry out once heat sampling, check geometrical dimension.Finishing temperature control is between 860 ~ 900 DEG C.The finishing temperature control of embodiment 1 ~ 4 is between 870 ~ 880 DEG C.
Step S8: reheat
Steel pipe after tandem rolling takes off pipe enters reheating furnace, and reheating furnace temperature controls between 900 ~ 930 DEG C.
Step S9: sizing or a tube reducing
Be rolled into through stretch-reducing mill (or sizing mill) weldless steel tube that external diameter and wall thickness meet the demands, after a tube reducing or sizing, body temperature controls between 830-880 DEG C, to reach effect of rolling normalizing.
Step S10: aligning, cooling and sawing
Perform band temperature correction straight, straightening temperature >=500 DEG C.Hot-rolled tube is delivered to cold bed, and adopt solid matter cloth, after slowly cooling to room temperature, sawing becomes specified length.It is as shown in table 3 that the straightening temperature of each embodiment and ring cutting method measure unrelieved stress.
The straightening temperature of each embodiment of table 3 and ring cutting method measure unrelieved stress
| Embodiment | Straightening temperature/DEG C | Ring cutting method measures unrelieved stress/MPa |
| 1 | 527 | 17 |
| 2 | 522 | 19 |
| 3 | 520 | 20 |
| 4 | 521 | 19 |
Step S11: flaw detection and chamfered edge
To steel pipe by Zhi Jinhang carrying out flaw detection and the water test, eligible carries out chamfered edge processing at two ends, finally obtains containing the resistance to H of rare earth
2s corroded pipeline weldless steel tube.The pipeline of embodiment 1 ~ 4 is L290NS pipeline.
The mechanics properties testing value of the seamless steel pipe for line pipe that embodiment 1 ~ 4 prepares, SSC performance, HIC performance and histological test result are respectively in table 4 and table 5.
Table 4 mechanical properties of pipe detected result
Table 5SSC performance/HIC performance/histological test result
| Embodiment | ﹡ SSC performance | ﹡ HIC performance | Tissue | Grain fineness number |
| 1 | Within 720 hours, sample does not rupture | ﹡CSR＝0，CLR＝0，CTR＝0 | F+P | 9.0 level |
| 2 | Within 720 hours, sample does not ftracture | ﹡CSR＝0，CLR＝0，CTR＝0 | F+P | 9.0 level |
| 3 | Within 720 hours, sample does not rupture | ﹡CSR＝0，CLR＝0，CTR＝0 | F+P | 9.0 level |
| 4 | Within 720 hours, sample does not ftracture | ﹡CSR＝0，CLR＝0，CTR＝0 | F+P | 9.0 level |
﹡ SSC performance: according to NACEStandardTM0177-2005 standard A method, adopts smooth tension specimen method, and test constant stress is 0.8Rt0.5, through H
2s saturated solution (solution A) successive soaking sample 720 hours.
﹡ HIC performance: according to NACEStandardTM0284-2003 standard A method, to sample solution A successive soaking 96 hours.
﹡ CSR: crack-sensitivity rate, CLR: crack length rate, CTR: crack thickness rate.
As can be seen from table 3 ~ table 5, prepared by the present invention contains the resistance to H of rare earth
2the mechanical property of S corroded pipeline weldless steel tube is as follows: yield strength is 320 ~ 380MPa, ring cutting method measures that unrelieved stress≤25MPa, tensile strength are 450 ~ 520MPa, yield tensile ratio≤0.80, unit elongation>=32%, traverse impact value are a
kV>=160J/cm (0 DEG C), shear than be 100%, hardness≤220HV10, grain fineness number>=8.5 grade.SSC performance: constant stress is 0.8R
t0.5=232MPa, through H
2s saturated solution (solution A) soaks continuous 720 hours, and sample does not rupture.HIC performance: CSR=0, CLR=0 and CTR=0.
Claims (2)
1. one kind contains the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube, is characterized in that, comprising: the production process of continuous casting circular tube blank and tubulation process; What prepare is described containing the resistance to H of rare earth
2the mass percentage of the chemical composition of S corroded pipeline weldless steel tube is: C0.06 ~ 0.12, Si0.05 ~ 0.30, Mn0.80 ~ 1.10, Cr0.10 ~ 0.30, Mo0.10 ~ 0.20, V0.03 ~ 0.10, Ti0.01 ~ 0.03, Al0.01 ~ 0.04, rare earth elements RE 0.0005 ~ 0.0100, Cu≤0.10, P≤0.015, S≤0.005, surplus is matrix Fe and impurity element, wherein, described rare earth elements RE comprise mass percentage be 67% Ce and mass percentage be the La of 33%; The production process of described continuous casting circular tube blank comprises: hot metal pretreatment, top and bottom combined blown converter smelting, the refining of LF stove, VD vacuum-treat, round billet continuous casting and cutting; Described hot metal pretreatment comprises: molten iron is done desulfating and deoxidation pre-treatment, makes mass percentage≤0.010% of the S in the molten iron after hot metal pretreatment; Described top and bottom combined blown converter smelting comprises: the molten iron after described hot metal pretreatment is blended into top and bottom combined blown converter, add steel scrap, the mass ratio of the molten iron after described hot metal pretreatment and described steel scrap is 9:1, single slag technique is adopted to smelt, controlling finishing slag basicity is 3.0, in tapping process, silicomanganese, ferromanganese and ferrochrome carry out deoxidation alloying, wherein, in every 100 tons of tapping molten steel, ferrosilicon is 260kg, ferromanganese is 1200kg, ferrochrome is 200kg, final deoxygenation adopts aluminium deoxidation technique, tapping process pushing off the slag or skim, described tapping molten steel adds lime block 200kg; The refining of described LF stove comprises: whole process blows Ar, adopts the mode improving heat-up rate gradually to heat temperature raising; Carry out making white slag desulfurization, composition adjustment and warming temperature according to the molten steel composition of described top and bottom combined blown converter smelting and temperature; Ferro-molybdenum 150kg, ferro-vanadium 100kg and ferro-titanium 100kg is added in the middle and later periods of LF stove refining every 100 tons of LF refined molten steel; The refining of described LF stove terminates rear maintenance bottom soft blow Ar, and feed 200 meters of rare-earth wires by predetermined add-on, described predetermined add-on is 0.02% of the quality of LF refined molten steel; Vacuum treated vacuum tightness≤the 0.10KPa of described VD, dark vacuum time>=13 minute, feeding fixed length silico-calcium silk, feeds silk after-blow Ar8 ~ 10 minute; Described round billet continuous casting and cutting comprise: the molten steel after VD vacuum-treat is carried out round billet continuous casting, adopt pulling rate fixed speed control and the induction stirring technique of 1.1m/min; Control molten steel overheat≤30 DEG C; After strand goes out the laggard row aligning in cooling twice region, then flame cutting is circular pipe blank; Described tubulation process comprises: heating of pipe blank, perforation, tandem rolling, reheat, sizing or tube reducing, aligning, cooling, sawing, flaw detection and chamfered edge; Described heating of pipe blank comprises: pipe is put into process furnace and heats, when the diameter of pipe is 180mm, heat two sections be 1260 ~ 1300 DEG C, soaking one section is 1260 ~ 1300 DEG C, soaking two sections is 1260 ~ 1300 DEG C; When the diameter of pipe is 270mm, preheated one-section is 1050 ~ 1120 DEG C, preheating two sections is 1150 ~ 1250 DEG C, heating one section is 1250 ~ 1290 DEG C, heating two sections is 1270 ~ 1300 DEG C, soaking one section is 1270 ~ 1300 DEG C, soaking two sections is 1270 ~ 1300 DEG C; The finishing temperature of described tandem rolling is 860 ~ 900 DEG C; Described reheating comprises: the steel pipe after described tandem rolling enters reheating furnace, and reheating furnace temperature is 900 ~ 930 DEG C; After described sizing or tube reducing, body temperature is 830 ~ 880 DEG C; Described aligning is that band temperature correction is straight, described band temperature straightening temperature>=500 DEG C.
2. as claimed in claim 1 containing the resistance to H of rare earth
2the preparation method of S corroded pipeline weldless steel tube, is characterized in that, what prepare is described containing the resistance to H of rare earth
2the mass percentage of the chemical composition of S corroded pipeline weldless steel tube is: C0.09, Si0.19, Mn0.95, Cr0.27, Mo0.13, V0.06, Ti0.017, Al0.025, RE0.0013, Cu0.007, P0.012, S0.003; Or, C0.10, Si0.21, Mn0.97, Cr0.25, Mo0.14, V0.05, Ti0.015, Al0.032, RE0.0012, Cu0.008, P0.013, S0.003; Or, C0.06, Si0.05, Mn1.10, Cr0.30, Mo0.20, V0.10, Ti0.01, Al0.04, RE0.01, Cu0.1, P0.015, S0.005; Or, C0.12, Si0.30, Mn0.80, Cr0.10, Mo0.10, V0.03, Ti0.03, Al0.01, RE0.0005, Cu0.1, P0.009, S0.002.
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| CN103667929A (en) * | 2013-11-27 | 2014-03-26 | 包头钢铁（集团）有限责任公司 | Low-cost and H2S-corrosion-resistant L390NS pipeline tube containing rare earth and production method of pipeline tube |
| CN104313470A (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 L485QO submerged pipeline and production method of seamless steel tube |
| CN105886719A (en) * | 2016-05-25 | 2016-08-24 | 内蒙古包钢钢联股份有限公司 | Method for controlling 16 Mn seamless steel tube blank heating |
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