CN103866187A - Steel plate for 500MPa-level pressure container for resisting sulfide stress corrosion cracking and production method thereof - Google Patents
Steel plate for 500MPa-level pressure container for resisting sulfide stress corrosion cracking and production method thereof Download PDFInfo
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Abstract
The invention relates to the field of manufacturing of a steel plate for a pressure container, and particularly relates to a steel plate for a 500MPa-level pressure container for resisting sulfide stress corrosion cracking and a production method thereof. The steel plate is prepared from the following components by mass percent: no more than 0.20% of C, 0.15-0.50% of Si, no more than 1.35% of Mn, no more than 0.012% of P, no more than 0.002% of S, no more than 0.10% of Nb, V and Ti, 0.020-0.050% of Alt, and the balance of Fe and inevitable impurities. The steel plate has the beneficial effects that each component is accurately controlled in the smelting process, the content of harmful elements such as P, S and the like in steel is strictly controlled, the cleanliness of molten steel is improved, a continuous casting blank is heated after being slowly cooled by a burial pit or a slow cooling cover, and the steel plate for the pressure container having the advantages of resisting sulfide stress corrosion cracking, hydrogen-induced cracking and lamellar tearing, high temperature resistance, being easy to weld, and the like is obtained by reasonably controlling slowly cooling and normalizing heat treatment processes of rolled and steel plates.
Description
Technical field
The present invention relates to steel heavy plate for pressure vessels and manufacture field, specifically refer to a kind of steel heavy plate for pressure vessels and production method thereof of 500MPa level resisting sulfide stress corrosion crack.
Background technology
Corrosion is that the security of transport, store oil (gas) tank plate is brought to one of principal mode of threat, cause often Plate break, bring out the root of catastrophic failure, and sulfide-stress cracking (SSCC) and two kinds of dissimilar corrosion crackings of hydrogen induced cracking (HIC) (HIC) are the principal modes that cause sulfur-containing gas, oil (gas) corrosion failure.Within the scope of the world today, on the one hand along with the day by day increase of human society to Sweet natural gas, oil (gas) demand, the higher Sweet natural gas of many sulfide hydrogens (H2S) composition, oil (gas) are exploited, carried and process; Along with the raising of pipeline delivery pressure and pressurized vessel reservoir pressure, also cause hydrogen sulfide sectional pressure to increase on the other hand.These factors will make SSCC, the HIC problem of conveying, store oil (gas) tank plate more outstanding, are to be also badly in need of at present one of subject matter solving.
At moistening hydrogen sulfide (H
2s), under envrionment conditions, in engineering, the carbon steel and low alloy steel of widespread use has the possibility that environmental cracking occurs.Sulfide-stress cracking (SSCC) and hydrogen induced cracking (HIC) (HIC) all belong to the steel cracking forms that wet hydrogen sulfide causes.The atomic hydrogen generating because of corrosion is easy to infiltrate in steel, and assemble in part, cause at the inner crackle of expanding along rolling direction that produces of steel, and in the time that interconnecting, adjacent crackle forms the seminess of the special shape that is transverse to thickness direction likeness in form ladder, be called hydrogen induced cracking (HIC) (being called for short HIC), or under the military service stress of steel superposes, acts synergistically, cause sulfide-stress cracking (being called for short SSCC).Wherein SSCC harm is maximum, and HIC and SSCC are also frequent and deposit.
In recent years, China has taked low-carbon (LC) (≤0.06%), super low sulfur (≤0.002%), calcium to process and the technological measure such as low coiled sheet coiling temperature in the productions such as high-strength line-pipe steel, Q345R, A516GR70, impact value and corrosion resistance are had significantly and improve, but also have a certain distance with external object performance level.Tracing it to its cause, except above-mentioned technological factor, is mainly to cause with the component segregation of continuously cast bloom crystallisation process on a small quantity that to be the secondary phase of short strip shape along rolling direction relevant when the rolling.
For improving component segregation of continuous casting slab, Japan and Germany all adopt the Clean Steel control techniques of phosphorus content≤0.01% sulphur content≤0.002%, the control technique that casting process has adopted induction stirring and strand gently to depress.
Baosteel and Wuhan Iron and Steel Plant are on the basis of hot metal pretreatment, external refining has been carried out optimizing largely, transforming, and adopt rational calcium to process inclusion modification technology, made the cleanliness factor of steel grade obtain significantly improving, eradicated the formation of crack bringing out due to inclusion.
The performance index of the anti-SSCC steel heavy plate for pressure vessels of 500MPa level require to be much higher than conventional steel heavy plate for pressure vessels, except meeting resisting sulfide stress corrosion crack, resistance against hydrogen cracking requirement, generally the banded structure to steel plate, inclusion, grain fineness number, hardness, low-temperature impact, tempering resistance, anti-lamellar tearing, drawing by high temperature, carbon equivalent etc. have corresponding requirements, will meet above requirement, production difficulty is very large simultaneously.
The steel heavy plate for pressure vessels of 500MPa level resisting sulfide stress corrosion crack, taking 16-36mm thickness specification as example, more than requirement lower yield strength reaches 325MPa, tensile strength requires 500-630MPa, elongation >=21%, 0～-30 DEG C of transverse impact KV2 >=41J(test temperature), 180 ° of d=2a clod washes are qualified.Above traditional performance requires slightly to reduce with the increase of steel plate thickness specification.In addition, conventionally require the threshold stress of resisting sulfide stress corrosion crack (SSCC) inspection to reach 80%SMYS(standard yield strength) the actual yield strength of 80%AYS(even) level.SSCC test requirements document is immersed in sample in supersaturation acidic solution in the situation that applying threshold stress, keep not rupturing for 720 hours, touchstone has NACE TM0177 and GB/T 4157, and does not have at present a kind of technique of the steel heavy plate for pressure vessels that can produce 500MPa level resisting sulfide stress corrosion crack.
Summary of the invention
The object of the present invention is to provide a kind of steel heavy plate for pressure vessels and production method thereof of 500MPa level resisting sulfide stress corrosion crack, the component segregation that the process combination such as Clean Steel control techniques of the present invention, the light Reduction Technology of strand intelligence and continuously cast bloom and twice slow cooling technology of steel plate have solved continuously cast bloom crystallisation process causes the problem that is on a small quantity the secondary phase of short strip shape along rolling direction in the time of rolling.
The present invention is achieved by the following technical solutions:
A kind of steel heavy plate for pressure vessels of 500MPa level resisting sulfide stress corrosion crack, component by following mass percent is prepared from: C :≤0.20%, Si:0.15-0.50%, Mn :≤1.35%, P :≤0.012%, S :≤0.002%, Nb+V+Ti :≤0.10%,, Alt:0.020-0.050%, all the other are Fe and inevitable impurity.
The steel heavy plate for pressure vessels of a kind of 500MPa level resisting sulfide stress corrosion crack of the present invention, its thickness is 14～70mm.
Operational path of the present invention is: hot metal pretreatment → converter → ladle argon-blown → LF → RH → continuous casting → strand the roll off the production line slow cooling → normalizing → flaw detection → cutting of the cold inspection of slow cooling → strand cold sending → strand heating → de-scaling → rolling → aligning → steel plate, sampling → sample simulation postweld heat treatment (SR) → inspection, mark → warehouse-in.
The concrete steps of the production method of the steel heavy plate for pressure vessels of described a kind of 500MPa level resisting sulfide stress corrosion crack are:
A) smelt: raw material molten iron is through the processing of KR molten iron pre-desulfurization, make Sulfur Content in Hot Iron content < 0.002%, converter smelting, after tapping, carry out Argon processing, argon blowing time 10 minutes, then feed aluminum steel, send into again LF refining furnace trimming, desulfurization again, then Fruit storage in RH refining furnace, make O≤0.0025%, N≤0.0045%, H≤0.0002%, further even composition, when processing, protect vacuum time at least 15 minutes, after finishing, processing utilize feeding wire machine feeding calcium iron wire to carry out Ca processing, after feeding calcium iron wire, molten steel is carried out stirring a little less than soft blow argon, churning time at least 15 minutes, argon flow amount 80～150L/min, molten steel stirs diameter 130-180mm,
B) continuous casting: continuous caster whole process protection cast on RH refining furnace molten steel after treatment, pulling rate 0.9m/min, in casting process, casting machine adopts the light soft reduction process of solidification end intelligence, after continuously cast bloom cutting, rolls off the production line immediately slow cooling to temperature≤200 DEG C, time is not less than 72 hours, obtains continuously cast bloom;
C) strand heating: strand is pressed 0.9～1.2min/mm at stove coefficient heat-up time; 1120～1180 DEG C of the tapping temperatures of strand;
D) rolling: strand goes out that process furnace adopts slightly after high-pressure water descaling, finish rolling temperature-controlled rolling stage by stage, 1100～1150 DEG C of roughing start rolling temperatures, adopt low speed to depress greatly rolling technology, ensure that the workpiece thickness of steel plate is finished product thickness 2～3 times, finish rolling start rolling temperature≤950 DEG C, 800～850 DEG C of finishing temperatures, roll rear steel plate and roll off the production line fast stacking slow cooling to room temperature;
E) thermal treatment: after steel plate slow cooling, adopt normalizing treatment technique, 890～910 DEG C of normalizing treatment temperature, steel plate normalizing time coefficient is by 1.5～1.8min/mm+15min, steel plate come out of the stove after naturally cooling, steel plate collecting temperature is less than 150 DEG C.
Above-mentioned steps (a) Raw molten iron requires P≤0.08%, As≤0.006%.
In above-mentioned steps (a), converter smelting adopts 210t top and bottom combined blown converter to smelt, and terminal target is pressed: C=0.06%-0.10%, P≤0.008%, S≤0.008%.
While tapping in above-mentioned steps (a), adopt scum rod, the two pushing off the slag tappings of floating plug, avoid lower slag, the tapping time is not less than 4 minutes.
In above-mentioned steps (a), be 1.6m/t with feeding aluminum steel speed.
In above-mentioned steps (a), calcium iron wire processing speed is 1.5m/t.
In above-mentioned steps (b) continuous casting process, slow cooling employing burial pit or slow cooling cover are cooling, and gained thickness of strand is 250mm.The retarded cooling process such as burial pit and slow cooling cover, is beneficial to separating out of hydrogen in steel.
Test check: be to ensure the welding property of steel plate, steel plate sample does simulation postweld heat treatment (SR) by user's requirement technique, when processing, temperature reaches 400 DEG C and takes on stove, and warming and cooling rate is no more than 150 DEG C/h.
The invention has the beneficial effects as follows: when the present invention smelts, each composition constituent element is precisely controlled, P in strict control steel, the harmful element content such as S, improve Cleanliness of Molten Steel, continuously cast bloom is through burial pit or slow cooling cover slow cooling post-heating, by rational controlled rolling, steel plate slow cooling and normalizing heat treatment technique, obtain having resisting sulfide stress corrosion crack, resistance against hydrogen cracking, anti-lamellar tearing, high temperature resistant, the steel heavy plate for pressure vessels of the advantages such as easy welding, (1) steel plate steel is pure, segregation is light, crystal grain is thin, stable performance, resisting sulfide stress corrosion crack performance and resistance against hydrogen cracking performance are good, (2) steel plate hardness is moderate, welding property is good, is beneficial to on-the-spot construction manufacture, (3) have good anti-lamellar tearing performance ,-30 DEG C of low-temperature flexibilities, more than 100J, have improved security, the reliability of materials'use greatly.
Brief description of the drawings
Fig. 1 is style schematic diagram before the embodiment of the present invention 1 steel plate resisting sulfide stress corrosion crack (SSCC) test;
Fig. 2 is the sample schematic diagram after the embodiment of the present invention 1 steel plate resisting sulfide stress corrosion crack (SSCC) test.
Embodiment
Further illustrate the present invention by following specific embodiment:
embodiment mono-
The steel heavy plate for pressure vessels of the 500MPa level resisting sulfide stress corrosion crack of the present embodiment is to be prepared from by the component of following mass percent: C:0.17%, Si:0.37%, Mn:1.29%, P:0.010%, S:0.001%, Nb+V+Ti :≤0.060%, Alt:0.035%, all the other are Fe and inevitable impurity, and wherein O, N, H content are respectively 0.0018%, 0.0035% and 0.00015%.
Finished steel plate thickness is 16mm.
The preparation method of described steel plate, comprises the following steps:
(1) hot metal pretreatment: raw material molten iron P=0.080%, S=0.024%, As=0.0020%, after through KR hot metal pretreatment, dark desulfurization is processed, molten iron S content is 0.0006%.
(2) converter smelting: in terminal composition: C=0.09%, P=0.0080%, S=0.0078%, adopts scum rod, the two pushing off the slag tappings of floating plug, 5 minutes tapping time, tapping process steel ladle full Argon when tapping.
(3) ladle argon-blown: tap complete, to Argon station Argon 10 minutes (containing tapping argon blowing time), with feeding wire machine hello aluminum steel (ф 13) 1.6m/t.
(4) LF+RH refining treatment: molten steel is sent into LF refining furnace trimming, desulfurization, then go up Fruit storage in RH refining furnace, evenly composition, RH protects vacuum time 17 minutes while processing, after processing finishes, utilize feeding wire machine feeding calcium iron wire 1.5m/t, after line feeding, molten steel is carried out stirring a little less than soft blow argon weak churning time 18 minutes, a little less than stir argon flow amount 100L/min, molten steel stirs diameter 150mm.
(5) continuous casting: 250 × 2200 straight arc billet continuous casting machine whole process protection cast on molten steel after refining; pulling rate 0.9m/min constant speed is drawn steel; in casting process, casting machine adopts the light soft reduction process of solidification end intelligence; after continuously cast bloom cutting, roll off the production line immediately into burial pit slow cooling to 180 DEG C; 76 hours slow cooling time, finally obtain the flawless continuous-casting billet that segregation is light, steel cleanliness factor is high, composition is qualified.
(6) strand heating: strand send recuperative heater heating, and at stove 250min heat-up time, strand tapping temperature reaches 1140 DEG C.
(7) rolling: strand goes out that process furnace adopts slightly after high-pressure water descaling, finish rolling temperature-controlled rolling stage by stage, 1130 DEG C of roughing mill start rolling temperatures, adopt low speed to depress greatly rolling technology, workpiece thickness 45mm after roughing.930 DEG C of finish rolling operation start rolling temperatures, 830 DEG C of finishing temperatures, roll rear steel plate and roll off the production line fast stacking slow cooling to room temperature.
(8) thermal treatment: adopt normalizing treatment technique after steel plate slow cooling.890 DEG C of normalizing treatment temperature, normalizing treatment in-furnace time 41min, individual keeps flat steel plate after coming out of the stove, naturally cooling, steel plate collecting temperature 50 C.
(9) sample simulation postweld heat treatment (SR): 610 DEG C for the treatment of temps, soaking time 4 hours, reaches 400 DEG C by temperature when processing and take on stove, 140 DEG C/h of heat-up rate, 130 DEG C/h of cooling rate.
embodiment bis-
The steel heavy plate for pressure vessels of the 500MPa level resisting sulfide stress corrosion crack of the present embodiment is to be prepared from by the component of following mass percent: C:0.18%, Si:0.36%, Mn:1.33%, P:0.009%, S:0.001%, Nb+V+Ti :≤0.090%, Alt:0.032%, all the other are Fe and inevitable impurity, and wherein O, N, H content are respectively 0.0023%, 0.0020% and 0.00013%.
Finished steel plate thickness is 42mm.
The preparation method of the steel heavy plate for pressure vessels of the 500MPa level resisting sulfide stress corrosion crack of the present embodiment is with embodiment mono-, difference is after hot metal pretreatment that S content is 0.0010%, in converter terminal composition, P, S content are respectively 0.0078% and 0.0075%, it is 15 minutes that RH stove is protected vacuum time, after RH station line feeding, the weak churning time of soft blow argon is 16 minutes, continuously cast bloom goes out 1150 DEG C of furnace temps, 1140 DEG C of roughing start rolling temperatures, workpiece thickness 90mm, 840 DEG C of finish rolling finishing temperatures, normalizing treatment in-furnace time is 83min.
embodiment tri-
The component of the mass percent of the steel heavy plate for pressure vessels of the 500MPa level resisting sulfide stress corrosion crack of the present embodiment is with embodiment bis-.
Finished steel plate thickness is 70mm.
The preparation method of the steel heavy plate for pressure vessels of the 500MPa level resisting sulfide stress corrosion crack of the present embodiment is with embodiment mono-, difference is after hot metal pretreatment that S content is 0.0010%, P in converter terminal composition, S content is respectively 0.0078% and 0.0075%, it is 15 minutes that RH stove is protected vacuum time, after RH station line feeding, the weak churning time of soft blow argon is 16 minutes, continuously cast bloom goes out 1160 DEG C of furnace temps, 1145 DEG C of roughing start rolling temperatures, workpiece thickness 140mm, 850 DEG C of finish rolling finishing temperatures, normalizing treatment in-furnace time is 127min, when sample simulation postweld heat treatment, warming and cooling rate is 135 DEG C/h.
Steel heavy plate for pressure vessels to the 500MPa level resisting sulfide stress corrosion crack of preparation in above embodiment mono-to three carries out performance test, as shown in table 1,2,3,4,5.
The intensity of steel plate and elongation surplus capacity are moderate, and low-temperature flexibility and thickness directional properties are good ,-30 DEG C of low-temperature flexibilities, more than 100J, meet correlation engineering service requirements completely, greatly improve security, reliability that this steel plate uses, and be beneficial to on-the-spot construction manufacture.
The anti-SSCC test of steel plate is carried out according to standard GB/T 4157-2006 " metal is anti-special shape environmental cracking laboratory test in hydrogen-sulfide environmental " A method, embodiment steel plate sample is all not fractures under test conditions, illustrate that this steel plate has good resisting sulfide stress corrosion crack performance.
The anti-HIC test of plate is undertaken by GB/T 8650-2006 " pipe line steel and pressure vessel steel resistance against hydrogen cracking assessment method ", and testing liquid is A solution.Crack length rate CLR, the crack width rate CTR of embodiment steel plate sample, CSR is good for crack-sensitivity rate, shows that this steel plate has stronger resistance against hydrogen cracking performance.
The steel of steel plate is pure, crystal grain is thin, has ensured that steel plate properties meets service requirements.
Above data show that the resistance to elevated temperatures of example steel plate is good.
Claims (9)
1. the steel heavy plate for pressure vessels of a 500MPa level resisting sulfide stress corrosion crack, it is characterized in that: the component by following mass percent is prepared from: C :≤0.20%, Si:0.15-0.50%, Mn :≤1.35%, P :≤0.012%, S :≤0.002%, Nb+V+Ti :≤0.10%, Alt:0.020-0.050%, all the other are Fe and inevitable impurity.
2. the steel heavy plate for pressure vessels of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 1, is characterized in that: described steel plate thickness is 14～70mm.
3. the production method of the steel heavy plate for pressure vessels of a kind of 500MPa level resisting sulfide stress corrosion crack according to claim 1, comprises the steps:
(a) smelt: raw material molten iron is through the processing of KR molten iron pre-desulfurization, make Sulfur Content in Hot Iron content < 0.002%, converter smelting, after tapping, carry out Argon processing, argon blowing time 10 minutes, then feed aluminum steel, send into again LF refining furnace trimming, desulfurization again, then Fruit storage in RH refining furnace, make O≤0.0025%, N≤0.0045%, H≤0.0002%, further even composition, when processing, protect vacuum time at least 15 minutes, after finishing, processing utilize feeding wire machine feeding calcium iron wire to carry out Ca processing, after feeding calcium iron wire, molten steel is carried out stirring a little less than soft blow argon, churning time at least 15 minutes, argon flow amount 80～150L/min, molten steel stirs diameter 130-180mm,
(b) continuous casting: continuous caster whole process protection cast on RH refining furnace molten steel after treatment, pulling rate 0.9m/min, in casting process, casting machine adopts the light soft reduction process of solidification end intelligence, after continuously cast bloom cutting, rolls off the production line immediately slow cooling to temperature≤200 DEG C, time is not less than 72 hours, obtains continuously cast bloom;
(c) strand heating: strand is pressed 0.9～1.2min/mm at stove coefficient heat-up time; 1120～1180 DEG C of the tapping temperatures of strand;
(d) rolling: strand goes out that process furnace adopts slightly after high-pressure water descaling, finish rolling temperature-controlled rolling stage by stage, 1100～1150 DEG C of roughing start rolling temperatures, adopt low speed to depress greatly rolling technology, ensure that the workpiece thickness of steel plate is finished product thickness 2～3 times, finish rolling start rolling temperature≤950 DEG C, 800～850 DEG C of finishing temperatures, roll rear steel plate and roll off the production line fast stacking slow cooling to room temperature;
(e) thermal treatment: after steel plate slow cooling, adopt normalizing treatment technique, 890～910 DEG C of normalizing treatment temperature, steel plate normalizing time coefficient is by 1.5～1.8min/mm+15min, steel plate come out of the stove after naturally cooling, steel plate collecting temperature is less than 150 DEG C.
4. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, is characterized in that: in described step a), raw material molten iron is the qualified molten iron of P≤0.08%, As≤0.006%.
5. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, it is characterized in that: in described step a), converter smelting adopts the two slag meltings of 210t top and bottom combined blown converter, converter terminal: C=0.06%-0.10%, P≤0.008%, S≤0.008%.
6. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, it is characterized in that: described step a) middle tapping adopts scum rod, the two pushing off the slag tappings of floating plug, tapping time >=4 minute.
7. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, is characterized in that: described step a) in feed aluminum steel speed be 1.6m/t.
8. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, is characterized in that: the described step a) speed of middle calcium iron wire processing is 1.5m/t.
9. the preparation method of the steel heavy plate for pressure vessels of a kind of tensile strength 500MPa level resisting sulfide stress corrosion crack according to claim 3, it is characterized in that, described step is b) in continuous casting process, and slow cooling adopts burial pit or slow cooling cover, and gained thickness of strand is 250mm.
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Application publication date: 20140618 |