CN100587098C - Micro-alloying steel for oil gas transport seamless pipeline and its preparation method - Google Patents
Micro-alloying steel for oil gas transport seamless pipeline and its preparation method Download PDFInfo
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Abstract
The invention discloses micro-alloying seamless pipeline steel and process for preparation. According to weight percentage, the range of the chemical components of the invention includes that C holds0.08% to 0.20%, Si is equal to or less than 0.04%, Mn takes 0.60% to 1. 50%, S is equal to or less than 0.015%, P is equal to or less than 0.025%, Al is equal to or less than 0.04%, Ti is equal to orless than 0.04%, H is equal to or less than 2.5*10-4%, O is equal to or less than 25*10-4%, the rest is Fe and unavoidable foreign matters. The process for preparation comprises technique steps, including smelting, refining, continuous casting, hot rolling and slow cooling. Round steel with the size of phi 70 to 150 millimeters can be produced by the process for preparation. The seamless pipelinesteel of the invention has perfect anti-sulphide stress corrosion (SSC resistance) capability and anti-HIC property. The pipeline steel which can substitute for welding pipe can be utilized in the filed of oil pipeline and the like, and the invention increases the reliability of material and adaptability of variety, in particular being adaptable for the low submarine temperature and corrosion-resistant environment and for manufacture of thick-walled tubes.
Description
Technical field
The present invention relates to metallurgical technology field, belong to the pipe line steel class.Relate to a kind of micro-alloying steel for oil gas transport seamless pipeline and manufacture method thereof, relate in particular to a kind of microalloying pipe line steel and manufacture method thereof that land and sea-bottom oil-gas line of pipes, high-pressure oil gas gathering line and high pressure water injection pipe, urban pipe network are built that be used to make.
Background technology
Along with carrying apart from high-pressure oil gas in exploitation, conveying and the land length of the unstable area of geological state, deep-sea oil gas, the exploitation of high pressure, high resistance to deformation line-pipes steel has become the focus of each manufacturer's development in recent years.At present, the transportation pipe alignment high-performance, the long lifetime direction develops.
When pipeline under the ocean required proof strength with weldless steel tube, plasticity and toughness were good, low-temperature performance is good, hydrogen sulfide corrosion resistant.Hydrogen sulfide corrosion mainly shows as hydrogen drum blister HB and hydrogen induced cracking (HIC) HIC two big classes, and it mainly is because the hydrogen in the environment for use causes after entering piping material.To the most deleterious non-ferrite+perlite tissue and banded structure, the weld seam junction of being organized as of hydrogen drum blister susceptibility and hydrogen induced cracking (HIC) HIC.Numerously adopt anti-deformation, low-temperature performance, the well behaved weldless steel tube of anti-HIC as tubing mostly at complex geological condition of building and planning to build or subsea pipeline.
At present, the steel of manufacturing pipe line steel are mainly welded tube pipeline steel plate.Compare with general purpose pipe line steel, seamless pipeline has following characteristics with pipe line steel: seamless pipeline is generally ferrite+pearlitic structure with pipe line steel, banded structure is slighter, can adopt box cupling connection, socket joint connection etc., avoided welded heat affecting zone tissue, performance inconsistency, and cold-and-heat resistent crack performance, anti-HIC excellent property.
CN1875121 discloses a kind of high strength stainless steel pipe for line pipe of excellent corrosion resistance, goods are that its composition contains in quality %: C:0.001～0.015%, Si:0.01～0.5%, Mn:0.1～1.8%, below the P:0.03%, below the S:0.005%, Cr:15.5～18%, more than the Ni:0.5%, less than 5.5%, Mo:0.5～3.5%, V:0.02～0.2%, N:0.001～0.015%, below the O:0.006%, and satisfy Cr+0.65Ni+0.6Mo+0.55Cu-20C 〉=18.5, Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N 〉=11.5, the steel pipe of C+N≤0.025.Preferably quench-temper.And can contain Al:0.002～below 0.05%.In addition, can contain and be selected among Nb, Ti, Zr, B, the W one or more and/or Cu and Ca.Organize and preferably contain martensite, ferrite, remaining γ.
CN1894434 discloses a kind of steel plate and superstrength line pipe and manufacture method thereof with excellent low-temperature toughness that is used for the superstrength line pipe, described steel plate comprises the C of 0.03 to 0.07 quality %, be no more than the Si of 0.6 quality %, 1.5 Mn to 2.5 quality %, be no more than the P of 0.015 quality %, be no more than the S of 0.003 quality %, 0.1 Ni to 1.5 quality %, 0.15 Mo to 0.60 quality %, 0.01 Nb to 0.10 quality %, 0.005 Ti to 0.030 quality %, be no more than the Al of 0.06 quality %, the B of one or more specified amounts, N, V, Cu, Cr, Ca, REM (rare earth metal) and Mg, remainder is made up of iron and unavoidable impurities, and the ratio of time (Hv-ave)/(Hv-M) is between 0.8 to 0.9 in 2.5≤P≤4.0, wherein Hv-ave is that average dimension formula hardness and Hv-M on the matrix metal thickness direction are the martensite hardness (Hv-M=270+1300C) that depends on C content, and tensile strength TS-C is between 900MPa and 1100MPa; P=2.7C+0.4Si+Mn+0.8Cr+0.45 (Ni+Cu)+(1+ β) Mo-1+ β (β=1 when B 〉=3ppm, and when B＜3ppm β=0).But CN1875121, CN1894434 patent of invention steel grade all contain noble metals such as Ni, Mo, and manufacturing cost is very high.
The line pipe that CN1914341 discloses the good pipe line steel of anti-HIC and produced with these steel, its composition contains 0.03～0.15% C, 0.05～1.0% Si, 0.5～1.8% Mn, the P smaller or equal to 0.015%, S, the O (oxygen) smaller or equal to 0.01% smaller or equal to 0.004%, the N smaller or equal to 0.007%, 0.01～0.1% Sol.Al, the Ti smaller or equal to 0.024%, 0.0003～0.02% Ca according to mass percent, all the other are made of Fe and impurity, and the size of the TiN that exists as inclusion in steel is smaller or equal to 30 μ m.The CN1914341 patent of invention contains 0.05～1.0% Si, and Si content is higher, reduces the toughness of steel, is unfavorable for the further raising of HIC performance; Ti exists as inclusion in steel, and the size of its TiN is smaller or equal to 30 μ m.
Summary of the invention
The present invention mainly processes service requirements according to the user, adopt eaf process to produce sea-bottom oil-gas transport seamless line steel, and satisfy the problem of anti-deformation, low-temperature performance, anti-HIC performance, provide a kind of and had that adaptability is strong, the micro-alloying steel for oil gas transport seamless pipeline and the manufacture method thereof of excellent combination property.
The invention provides the seamless pipe line steel of a kind of microalloying, it is characterized in that, it forms by weight that percentage ratio is:
C:0.08～0.20%, Si :≤0.40%, Mn:0.60～1.50%, S≤0.015%, P≤0.025%, Al≤0.04%, Ti≤0.04%, H :≤2.5 * 10
-4%, 0 :≤25 * 10
-4%, surplus is Fe and unavoidable impurities.
Preferably, the seamless pipe line steel of microalloying is characterized in that, it forms by weight that percentage ratio is:
C:0.08～0.20%, Si:0.17～0.35%, Mn:0.80～1.20%, S≤0.010%, P≤0.020%, Al≤0.040%, Ti≤0.04%, H :≤2.5 * 10
-4%, O :≤20 * 10
-4%, surplus is Fe and unavoidable impurities.
The present invention also provides the manufacture method of described pipe line steel, comprise smelting, refining, continuous casting, hot rolling, retarded cooling process step, it is characterized in that, smelt and alloying: electrosmelting, slag free tapping, adopt external refining, vacuum outgas to handle to chemical ingredients and meet the requirements, hydrogen richness is not more than 2.5 * 10 in the steel
-4%, oxygen level are not more than 25 * 10
-4%; Continuous casting, control superheating temperature superheating temperature are that 10～30 ℃, pulling rate are 0.50～0.85m/min; Hot rolling: strand is 1130～1280 ℃ in the Heating temperature of process furnace, 1100～1500 ℃ of start rolling temperatures, finishing temperature=850～980 ℃; Roll the back slow cooling, speed of cooling is 0.1～1 ℃/min.
Preferably, described refining is the LF+VD refining, it is characterized in that, adopt hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology, the abundant pre-deoxidation of electric furnace steel tapping, LF adopts SiC and calcium-silicon compound deoxident diffusive deoxidation to keep white slag to replace hello aluminum steel deoxidation refining period, and argon gas fully stirs, and by feeding CaSi line aluminate is carried out denaturing treatment.
The present invention also provides the manufacture method of described pipe line steel, comprises smelting, refining, continuous casting, hot rolling, retarded cooling process step, it is characterized in that:
1) smelt and alloying: electrosmelting, slag free tapping, adopt external refining, vacuum outgas to handle that gas content meets the requirements to chemical ingredients and the steel, hydrogen richness is not more than 2.5 * 10 in the steel
-6, oxygen level is not more than 25 * 10
-6
2) LF+VD refining, adopt hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology, the abundant pre-deoxidation of electric furnace steel tapping, LF adopts SiC or calcium-silicon compound deoxident diffusive deoxidation to keep white slag to replace hello aluminum steel deoxidation refining period, big argon flow amount fully stirs, promote reaction of slag steel and deoxidation products collision to assemble, eliminate or minimizing chain aluminate, thereby aluminate enrichment in the minimizing process of setting, by feeding CaSi line aluminate is carried out denaturing treatment, improve the working plasticity of oil well tube blank steel, reduce the body surface imperfection.
Hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology adopt known smelting process, as described in " steel-making " 2006 22 volumes the 2nd phase 10-13 page or leaf.Described composite deoxidant is SiC powder and calcium-silicon compound deoxident.The technical requirements of silicon carbide reductor: SiC 〉=90%, C dissociates≤0.5%, Si+SiO
2≤ 2.5%, moisture≤0.5%.Silico-calcium reductor technical requirements: Ca 〉=30.0%, Si:25.0～30.0%, C≤1.0%, P≤0.04%, S≤0.10%.
2) continuous casting, the control superheating temperature is that 10～30 ℃, pulling rate are 0.50～0.85m/min, guarantees slab quality;
3) rolling: continuously cast bloom is 1130～1280 ℃ in the Heating temperature of process furnace, 1100～1500 ℃ of start rolling temperatures, finishing temperature=850～980 ℃.
4) slow cooling: roll the back slow cooling, speed of cooling is 0.5～1 ℃/min.
But adopt the round steel of this manufacture method production specification Φ 70～150mm.By taking the steel grade design and the rational technological measure of low-carbon-equivalent, microalloying, realized crystal grain thinning effectively, improved targets such as steel pipe plasticity and toughness, low-temperature performance, weldability.
The present invention also provides the described microalloying round steel that seamless pipeline steel is made.
The characteristics of technical solution of the present invention:
1, the X42 pipe line steel with widespread use at present compares
(1) steel of making pipe line steel at present are mainly welded tube pipeline steel plate.Compare with general purpose pipe line steel, this steel has following characteristics: metallographic structure is ferrite+perlite, banded structure is slighter, can adopt box cupling connection, socket joint connection etc., welded heat affecting zone tissue, performance inconsistency have been avoided, and cold-and-heat resistent crack performance, anti-HIC excellent property, butt joint performance are good, and site operation is convenient, can increase work efficiency.Be applicable to seabed, the various occasions in land.
(2) adopt hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology, guarantee that the deoxidation of the molten steel degree of depth, desulfurization reach and fully degas, go to be mingled with, reduce gas and non-metallic inclusion content in the steel, purify steel, prevent simultaneously aluminium deoxidation product in the steel and residue thereof cause steel creep brittleness, reduce the hot strength of steel; Guarantee the good thermal pressure processing characteristics of steel.
(3) LF adopts composite deoxidant and wire-feeding technique to replace hello aluminum steel deoxidation refining period, by eliminating or minimizing chain aluminate, thereby aluminate enrichment in the minimizing process of setting, by aluminate is carried out denaturing treatment, improve the working plasticity of oil well tube blank steel, reduce the body surface imperfection.
(4) adopt Al, Ti micro-alloying technology, guarantee tiny, the homogeneous microstructure of steel crystal grain; Adopt liquid iron charging and slag free tapping technology, guarantee that impurity and harmful residual element content are low in the steel; Guarantee that steel have good anticorrosive, anti-HIC performance; Give full play to yardstick below 10 μ m, the beneficial effect of tiny TiN second phase particle crystal grain thinning in seamless tube.Usually adopt Nb, V microalloying to compare with pipe line steel, this steel low cost of manufacture, crack sensitivity reduces, high-temp plastic is good.Electrosmelting adopts the quick decarburization of high temperature, smelting endpoint control techniques (TPC), strengthens pre-deoxidation technology, slag free tapping, fully degass, goes to be mingled with.Hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology are adopted in the LF+VD refining, guarantee that the deoxidation of the molten steel degree of depth, desulfurization reach and fully degas, go to be mingled with, and reduce gas and non-metallic inclusion content in the steel, purify steel.Continuous casting adopts low overheat, high liquid level (HLL), permanent pulling rate, non-oxidation protection cast, induction stirring, efficient covering slag, two cold weak gordian techniquies such as cold etc., guarantees that casting billet surface and interior tissue are good.
(5) adopt narrow Composition Control technology, with carbon content be controlled at lower limit, manganese content is controlled at middle limit, increases the polygonal ferrite amount, eliminates abnormal structures such as netted F and bainite, guarantee that seamless tube obdurability and the processing use properties made are good, satisfy terminal user's service requirements.
(6) this steel has high over-all properties, and its physical and chemical index has reached X46 and X52 grade of steel can realize that a steel uses more.
2, the manufacturing of steel
Take the fine fodder principle, select cleaning, few rust, drying and low-sulfur, low-phosphorous, high-quality steel scrap and former material auxiliary material that residual element are few for use.Electrosmelting adopts the quick decarburization of high temperature, smelting endpoint control techniques (TPC), strengthens pre-deoxidation technology, slag free tapping, fully degass, goes to be mingled with.Hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology are adopted in the LF+VD refining, guarantee that the deoxidation of the molten steel degree of depth, desulfurization reach and fully degas, go to be mingled with, and reduce gas and non-metallic inclusion content in the steel, purify steel.Continuous casting adopts low overheat, high liquid level (HLL), permanent pulling rate, non-oxidation protection cast, induction stirring, efficient covering slag, two cold weak gordian techniquies such as cold etc., guarantees that casting billet surface and interior tissue are good.Rolling, strand is 1130～1280 ℃ of process furnace Heating temperatures, start rolling temperature 〉=1100 ℃, and finishing temperature=850～980 ℃ guarantee that stocking crystal grain is tiny evenly, surface quality is good.Roll the back slow cooling, speed of cooling is 0.5～1 ℃/min; But adopt the round steel of this manufacture method production specification Φ 70～150mm.
Embodiment
Steel of the present invention is to adopt UHP (ultra high power) electric furnace+LF (ladle refining)+VD (vacuum outgas) technology smelting-continuous casting-heating-750 milling train to become a useful person-retarded cooling process production steel.Embodiment is as follows:
1. chemical ingredients
Pipe line steel of the present invention contains following composition.The per-cent of alloying element is meant mass percent.
C：0.08～0.20％
C is an effective element of strengthening steel, keeps necessary strength for making pipe line steel, makes the following of C content be limited to 0.08%.On the other hand, the excessive interpolation of C can make the hardness rising of line pipe, plasticity and toughness and weldability descend, and causes SSC easily.Simultaneously, polar region pipeline and off-shore pipeline have caused C content to reduce gradually to the needs of low-temperature flexibility, fracture resistance and ductility and plasticity.The development of micro-alloying technology makes pipe line steel keep high obdurability when carbon content reduces.Thereby, make C content on be limited to 0.20%.Take all factors into consideration anti-HIC performance of pipe line steel and embrittlement of grain boundaries, best C content is 0.10～0.18%.
Si：≤0.40％
Si is a deoxidant element in the steel, just lacks deoxidation effect when Si contains quantity not sufficient 0.05%.Therefore, establishing Si content lower value is 0.05%, and on the other hand, when interpolation Si was extremely excessive, the toughness of steel descended.The Si upper content limit is 0.40%.Preferably Si content is 0.15～0.25%.
Mn：0.60～1.50％
Mn is an effective element of strengthening steel.For making line pipe keep necessary strength, make the following of Mn content be limited to 0.60%.The raising of Mn content can improve the over-all properties of steel, because Mn can reduce the transformation temperature (reducing austenitic decomposition temperature) of the γ-α of steel, thereby ferrite crystal grain refinement and pearlite colony is diminished, and pearlite interlaminar spacing reduces, Fe
3The reduced thickness of C sheet, these all help improving the toughness of steel.An amount of manganese plays solution strengthening, refined crystalline strengthening and phase transformation strengthening, raising toughness, reduces the effect of the ductile-brittle transition temperature of steel.On the other hand, when adding Mn when excessive, the segregation of Mn is remarkable, and forming bainite etc. in the segregation portion of Mn has and can become the sclerotic tissue that HIC produces reason.Thus, making the Mn upper content limit is 1.30%.Preferably Mn's is 0.80～1.20% by stove.The pipe-line steel of this trial-production, Chemical Composition take C content to control by lower limit, and Mn content so both can satisfy the requirement of strength of user to this steel pipe by the measure of upper limit control, can satisfy again the requirement of steel pipe flexible.
S≤0.015％
S is an impurity element in the steel, and it promotes segregation, increases the crack sensitivity of steel, makes anti-HIC performance, anti-SCC performance, plasticity and toughness variation.S＜0.0015% o'clock, HIC obviously reduces.Pipe line steel requires the sulphur content in the steel very low usually, to guarantee good performances such as anti-HIC.Sulphur content can weaken the center segregation degree effectively in the reduction steel.Therefore, preferably S content is low.S content is restricted to≤0.015%.Preferably be restricted to≤0.010%.
P≤0.025％
P is an impurity element in the steel, and it promotes center segregation, and anti-HIC performance, low-temperature flexibility, welding property are significantly reduced; Improve the brittle transition temperature of steel, it is cold short that steel pipe is taken place.Therefore, preferably P content is low as far as possible.Thereby, P content is restricted to≤0.025%.
Al≤0.04％
Al is the bioelement that makes steel-deoxidizing.The compound action of Al and Ca can make TiN diminish.Al still is the element of crystal grain thinning commonly used in the steel, and the refinement homogenizing of ferrite crystal grain is played effective function, in order to bring into play these effects of Al, makes that the following of Al content is limited to 0.01% in the steel.On the other hand, when excessively adding Al, the purity of steel and toughness reduce, and cause the decline of watering property of molten steel, anti-HIC degradation easily.Therefore, making the higher limit of Al content is 0.04%.Preferably making Al content is 0.010～0.025%.
Ti≤0.04％
One of effect of microalloy element Ti is to stop austenite crystal to be grown up.Titanium content is 0.04% o'clock, and the grain coarsening temperature is brought up to about 1050 ℃.In strand, heating of pipe blank process, not molten microalloy carbon, nitride will obviously stop AUSTENITE GRAIN COARSENING by the mechanism of particle pinning crystal boundary.Another effect is the recrystallize that postpones γ in the operation of rolling.The microalloy carbonitride that the strain inducing precipitation is separated out in the operation of rolling can stop the recrystallize of deformation γ significantly by the effect of particle pinning crystal boundary and subgrain boundary, thereby obtains tiny phase-change organization by the phase transformation by not crystallization γ generation.Practice shows: the aluminium deoxidation Clean Steel contains 0.02%Ti and just can obtain fine grain structure (mean grain size is about 8 grades).Contain an amount of titanium and aluminium in the steel, its compound action is for refine austenite crystal grain, and it is more effective to improve the grain coarsening temperature.Simultaneously trace Ti can also form TiS, and macrobead MnS separates out, refinement MnS inclusion thereby reduce, significantly improve steel toughness, avoid the brittle transition temperature of steel to raise.The fusing point of TiN is very high, still can suppress grain growth at welded heat affecting zone, improves the anti-H of steel
2The S stress corrosion performance.On the other hand, when interpolation Ti is extremely excessive, the TiC amount that forms is more, thicker TiN particle occurs in the steel, hardening capacity, intensity and the fatigue strength of steel have been reduced, also reduce steel in the austenitic area high-temp plastic of (750～1000 ℃ of temperature ranges), this also is that strand or stocking are prone to one of reason of crackle.Along with the raising of the purity of steel, in the steel harm of TiN inclusion obvious more, easily cause crackle, the fatigue lifetime of reducing steel in processing and when using.Therefore, making the higher limit of Ti content is 0.04%.Because titanium content is low, it is very little that titanium is mingled with quantity; The titaniferous amount is 0.03% when following in the steel, and it is very little that titanium is mixed in the inclusion total amount proportion; When surpassing 0.03%Ti, titanium is mingled with quantity to begin to increase; Titanium is mingled with to account for and is mingled with 4.58% of total amount in the steel when containing 0.05%Ti.Preferably making Ti content is 0.01～0.02%.
H：≤2.5×10
-4％
H is an impurity element in the steel, and the purity of steel is descended.Be easy to cause the defectives such as white point, hydrogen embrittlement of steel, the massfraction of the hydrogen in the pipe line steel is high more, and the probability that HIC produces is big more, and corrosion rate is high more, and the increase of average crack length is remarkable more, thereby the toughness of steel, anti-HIC performance are significantly reduced.Therefore, H content is preferably low as far as possible.Thereby H content is restricted to≤2.5 * 10
-4%.Preferably be restricted to≤2.0 * 10
-4%.
O：≤25×10
-4％
O is an impurity element in the steel, and the purity of steel is descended.Cause anti-HIC performance, fatigue property, the low-temperature flexibility of steel to descend.Therefore, O content is preferably low as far as possible.Thereby O content is restricted to≤25 * 10
-4%.Preferably be restricted to≤20 * 10
-4%.
In addition, all the other are made of Fe, but may contain unavoidable impurities because of a variety of causes of manufacturing processed.
The pipe line steel of present embodiment also contains micro-Ca as required.Ca is the bioelement that is used for deoxidation, inclusion modification processing, and micro-Ca (about Ca/Al=0.10～0.15) is useful for the anti-HIC performance that improves steel.The compound action of Ca and Al can make TiN diminish.
2. manufacture method
Because oil, natural gas source are usually located at area outlying and that environment is abominable, line of pipes pressure is big, medium is complicated and be corrosive, and the assembly unit boxing of pipeline is generally carried out in the open air, this not only requires pipe line steel to have higher intensity, and require that good plasticity and toughness, anti-fatigue performance, anti-fracture characteristics and corrosion resistance nature are arranged, also require the improvement of mechanical property can not worsen the processing characteristics of steel simultaneously.The recent tendency of senior pipe line steel development is: high pure, high strength, high tenacity, weldability reach high corrosion resistance by force.Therefore; need to optimize all multifactor of external refining, each link of continuous casting in the pipe line steel production; carry out the exploitation of compound smelting technology; start with from all many-sides such as eaf tapping point control system, deep deoxidation system, slagging regime, refining slag Composition Control technology, ladle feeding line system, induction stirring system, vacuum-treat system, narrow Composition Control technology, protection cast systems and to further investigate, so that further improve the smelting technology route of high-cleanness, high pipe line steel.Electrosmelting, take the fine fodder principle, select cleaning, few rust, drying and low-sulfur, low-phosphorous, high-quality steel scrap and former material auxiliary material that residual element are few for use, smelting process adopts the quick decarburization of high temperature, terminal point control techniques (TPC), strengthens pre-deoxidation technology, slag free tapping mode, and fully degassing is mingled with.The LF+VD refining guarantees that the deoxidation of the molten steel degree of depth, desulfurization reach and fully degas, go to be mingled with, and reduces gas and non-metallic inclusion content in the steel, purifies steel.Continuous casting adopts low overheat, high liquid level (HLL), permanent pulling rate, non-oxidation protection cast, induction stirring, efficient covering slag, two cold weak gordian techniquies such as cold etc., guarantees that casting billet surface and interior tissue are good.
2.1 the control of purity of steel
Purity of steel control mainly is the control to steel inclusion, detrimental impurity element.Being mingled with in the aluminium deoxidation molten steel is mainly Al
2O
3, so control device is mainly reduction molten steel dissolved oxygen, the effect of enhancing refining, continuous casting working procedure removal inclusion.
The removal of oxygen and the control of inclusion thereof.The complicacy of oxygen is in the molten steel cools process of setting in the steel, and the solubleness reduction because of oxygen will further generate deoxidation products, and molten steel can form large inclusions with atmosphere, the anti-material generation of slag oxidizing reaction because of secondary oxidation in casting cycle.The quantity of steel inclusion, size, distribution, shape, type all will produce very big influence to the performance of steel.Brittle inclusion in the steel is to cause a lot of steel grades the reason of defective to occur.Reduce the The amount of inclusions that is generated and at first must reduce the eaf tapping point oxygen level, the system that reasonably blows is particularly stopped peroxidation, helps to reduce the endpoint molten steel oxygen level.By setting up effective cooperation of terminal control model and secondary refining technology, control oxygen content in steel≤0.0025%, wherein 95% heat oxygen level≤0.0020%.
Because residual aluminum can cause the creep brittleness of pipe line steel in the reaction product of aluminium deoxidation and the steel, cause the hot strength of steel to reduce, and reduce the fatigue property of pipe line steel; In addition, casting billet surface and the subcutaneous Al that gathers
2O
3Inclusion causes easily that outside fold defect appears in steel tube surface in the tube rolling process, so require to guarantee on the steel liquid deoxidation good basis acid-soluble aluminum content＜0.025% in the control steel.Study the tap Changing Pattern of aluminium and acid-soluble aluminum content in the VD steel of LF for this reason, developed low aluminium hypoxemia Clean Steel smelting technology technology.Through producing actual groping, acid-soluble aluminum content is more satisfactory between being controlled at 0.010～0.030% in going into VD stokehold steel.
In the past, the removal of hydrogen mainly realized by the fierce boiling of CO at the steel-making initial stage.The humidity of each operation slag former, alloy material, insulating covering agent and anti-material is stopped in strictness, avoids hydrocarbon polymer to contact with molten steel with air, is the effective ways that reduce hydrogen richness in the steel.Adopt the vacuum-treat technology, hydrogen can be stablized and is controlled at below 0.00025% in the steel.Field control VD vacuum tightness≤67Pa can make that hydrogen richness is lower than 0.00018% in the steel hold-time greater than 12 minutes.
The thermodynamic condition of desulfurization is high temperature, high basicity, low oxidisability.Therefore should guarantee for the realization deep desulfuration: oxygen level high basicity slag, slag low, the high sulfur capacity of use mixes in molten metal and the slag.The control of sulphur mainly is the comprehensive several means such as heating slag making, line feeding, vacuum, air blowing stirring that adopt when external refining in the pipe line steel.In addition, the long strip shape in the steel (especially distributing along crystal boundary) sulfide is the prerequisite that produces hydrogen induced cracking, molten steel is carried out calcification processing it can be changed into sphere, reduces its harm.
The removal of phosphorus mainly is to carry out at electrosmelting, tapping process.Fusing shifts to an earlier date slag making reinforcement dephosphorization latter stage, and the furnace bottom Argon increases the slag-metal reaction contact area, gives full play to the dephosphorizing capacity of high basicity slag.Electric furnace adopts the big quantity of slag and stays steel to stay slag operation, optimizes dephosphorization and prevents rephosphorization.
The existence of nitrogen in steel can reduce toughness, the welding property of steel, and steel fragility is increased, and also causes the continuously cast bloom cracking easily.For reducing the hazardous property of nitrogen, except that taking control nitrogen measures such as the heating of the omnidistance making foamed slag submerged arc of LF refining process, the stirring of omnidistance Argon, vacuum denitrification, the casting of casting process whole process protection, add insulating covering agent in the tundish, add covering slag in the crystallizer, big bag long nozzle, submerged nozzle blowing argon prevent absorption of nitrogen by steel and secondary oxidation; Adopt micro-alloying technology, make that residual nitrogen changes the second phase particle refinement crystal grain in the steel.
In addition, harmful elements such as Pb, Sb, As, Sn, Bi in the strict control steel of pipe line steel are in order to avoid cause the plasticity and toughness and the hot strength of weldless steel tube surface crack and reduction steel.Residual element such as Zn, Pb, Sb have higher vapour pressure in the steel, and easily evaporation and removing is easily to remove element under the steel-making temperature; And elements such as Cu, Sn are difficult to remove with normal method for making steel because its oxidation potential energy is lower than ferro element, need adopt an effective measure.Adopt the fine fodder principle: select for use molten iron and steel scrap surrogates such as high duty pig iron, DRI more than 40% that it is carried out " dilution " processing, make full use of the electric furnace hot metal charge and reduce residual element content.
2.2 calcification processing
The inclusion interface is strong hydrogen trap, is the source of crackle, and inclusion is many more, its HIC susceptibility maximum, and hydrogen induced cracking (HIC) is serious more.In order to improve the hydrogen-induced cracking resistance energy of material, should control inclusion content and form.In addition, in order to guarantee molten steel good casting properties is arranged, an amount of silicon-calcium wire of Xiang Gangzhong feeding carries out calcification processing.The feeding silicon-calcium wire very little or too much all can not get the ideal treatment effect.When calcium contents is too low, can not form low-melting calcium aluminate with aluminum oxide, formation be still dystectic complex inclusion, this moment is poorer than the steel casting properties that does not carry out the calcium processing.Calcium contents is too high, and sulphur content then can form dystectic CaS when also higher, worsens the casting properties of molten steel equally.When aluminium in the steel during, the disposable feeding silicon-calcium wire of refining 100m/ stove, and suitably regulate according to practical condition in 0.010～0.030% scope.After feeding silicon-calcium wire, carry out stirring and the calmness of for some time, inclusion is fully floated, otherwise can worsen the performance of covering slag in the casting process, bring detrimentally affect for production and equipment.
2.3 pipe line steel machinery, processing performance control
Pipeline under the ocean weldless steel tube desired strength height, plasticity and good toughness, welding property is good, can be-30 ℃ of safe handlings down.X42～X46 pipe line steel is had relatively high expectations to tissue, the obdurability of steel pipe, quality problems such as steel pipe often occurs that intensity is low, toughness does not conform to, mixed crystal, work-ing life are low.In order to improve the use properties of X42～X46 grade of steel oil pipeline steel pipe, technological measures such as the steel grade design of low carbon equivalent micro-alloyization and narrow composition control in the smelting process of steel, have been taked, pay close attention to the ingredient stability of carbon, manganese and microalloy element, thereby material property is tended towards stability, realized stable welding zone matrix on every side effectively, containment weld metal zone hard generates and crystal grain thinning mutually, improves targets such as toughness plasticity, guarantees that the body mechanical performance index is reliable and stable.
Toughness is the performance index of line pipe most critical, and the intensity and the plasticity of itself and steel all have relation.X42～46 pipe line steel matrix all are that the cable body adds a small amount of perlite, and metallographic structure is easy to occur ferrite network, a small amount of bainite etc., and all there is infringement in these abnormal structures to toughness.Adopt technology such as low-carbon microalloyed, structure refinement can solve the welding of X42 steel pipe box cupling ,-30 ℃ of impelling strength requirements simultaneously.
Suitably improve Mn/C, increase the polygonal ferrite amount, eliminate abnormal structures such as netted F and bainite; By sulphur, phosphorus and Mn/S ratio in the strict control molten steel, adopt Al-Ti combined microalloying crystal grain thinning simultaneously, improve plasticity and toughness; In order to improve the transverse impact performance of steel, add the Si-Ca composite core-spun yarn, implement inclusion modification and handle, further improve the toughness plasticity of steel pipe, reduce influence to pipe processing use properties.
Carry the prolongation of the natural gas line of sulfur-bearing and moisture along with active time, the weld seam position has the tendency that the fragility explosion takes place.The solid solubility of carbon in matrix stablized the welding zone tissue with the 2nd phase particle a large amount of and equally distributed, that have better high-temperature stability when utilizing strong carbide forming element Ti to stablize the shock heating Quench of welding zone, improves and guarantee the weldability and the postwelding performance of material.
The operation of rolling is controlled slab heating temperature, start rolling temperature, finishing temperature well, makes pipe line steel crystal grain tiny evenly, guarantees that stocking machinery, processing use properties are good.
2.3 anti-HIC Properties Control
Hydrogen sulfide corrosion mainly shows as hydrogen drum blister HB and hydrogen induced cracking (HIC) HIC two big classes, and it mainly is because the hydrogen in the environment for use causes after entering piping material.Studies show that both at home and abroad: to the most deleterious abnormal structure and the banded structure such as martensite of being organized as of hydrogen drum blister susceptibility and hydrogen induced cracking (HIC) HIC: 1. along with the increase of martensite volume, anti-HIC performance descends gradually, this mainly is to become hydrogen molecule because hydrogen atom is easily assembled at the martensite place, produce bigger interior pressure, it is very big to add the structural stress of martensite own, thereby very easily produce hydrogen drum blister and hydrogen induced cracking at this tissue place, influence anti-HIC performance.If want to improve the anti-HIC performance of material under hot-rolled state, must control its final metallographic structure, be advisable not produce quenching form martensitic stucture.2. banded structure is very big to the anti-HIC Effect on Performance of line pipe, and when banded structure rank 〉=2, anti-HIC performance index all exceed the scope of standard code.
In having the environment of H2S, cause hydrogen embrittlement in the hydrogen intrusion steel owing to the corrosion reaction generation.Improving aspect the anti-sulphide stress corrosion of pipe line steel (anti-SSC), it is effective obtaining uniform martensitic stucture and making grain-size when quenching tiny.Reduce in addition that the interaction of hydrogen and defective can improve anti-SSC performance in the steel.Can improve the anti-HIC of pipe line steel, anti-SSC performance by following measure: (1) improves the purity of steel; (2) improve composition and homogeneity of structure, when reducing sulphur content, carry out calcium and handle, the restriction banded structure; (3) crystal grain thinning; (4) reduce carbon content, control Mn content adds Ti, Ca etc. as far as possible.
But adopt the round steel of this manufacture method production specification Φ 70～150mm.
Embodiment 1:
The manufacture method of pipe line steel comprises smelting, refining, continuous casting, hot rolling, retarded cooling process step, it is characterized in that:
1) smelt and alloying: electrosmelting, slag free tapping, adopt external refining, vacuum outgas to handle that gas content meets the requirements to chemical ingredients and the steel, hydrogen richness is not more than 2.5 * 10 in the steel
-6, oxygen level is not more than 25 * 10
-6
2) hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology are adopted in LF+VD refining, guarantee that the deoxidation of the molten steel degree of depth, desulfurization reach and fully degas, go to be mingled with, and reduce gas and non-metallic inclusion content in the steel, purify steel.
Hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology adopt known smelting process, as described in " steel-making " 2006 22 volumes the 2nd phase 10-13 page or leaf.Difference is:
LF adopts SiC and calcium-silicon compound deoxident and CaSi line wire-feeding technique to replace hello aluminum steel deoxidation refining period, eliminate or minimizing chain aluminate, thereby aluminate enrichment in the minimizing process of setting, tapped preceding 3 minutes, feed the titanium heart yearn earlier, feed the CaSi line again, by feeding CaSi line aluminate is carried out denaturing treatment, look acid-soluble aluminum content feeding CaSi line 100～150m/t steel in the steel, control Ca/Al=0.10～0.15 guarantees that the Al2O3 inclusion modification becomes the higher spherical low melting point calcium-aluminate of calcium content and is mingled with (as 12CaO*7Al
2O
3), the working plasticity of raising oil well tube blank steel reduces the body surface imperfection.
2) continuous casting, the control superheating temperature is that 10～30 ℃, pulling rate are 0.50～0.85m/min, guarantees slab quality;
3) rolling: continuously cast bloom is 1130～1280 ℃ in the Heating temperature of process furnace, 1100～1500 ℃ of start rolling temperatures, finishing temperature=850～980 ℃;
4) slow cooling: roll the back slow cooling, speed of cooling is 0.5～1 ℃/min.
Concrete parameter sees Table 1 and table 2.
Table 1 pipe line steel embodiment chemical ingredients (weight, %)
| Specimen coding | C | Si | Mn | S | P | Al | Ti |
| 1 | 0.10 | 0.35 | 1.20 | 0.008 | 0.015 | 0.03 | 0.015 |
| 2 | 0.12 | 0.30 | 0.90 | 0.010 | 0.025 | 0.02 | 0.030 |
| 3 | 0.15 | 0.20 | 0.85 | 0.003 | 0.010 | 0.01 | 0.025 |
| X42 | 0.08～ 0.20 | ≤ 0.40 | 0.6～ 1.50 | ≤ 0.015 | ≤ 0.025 | ≤ 0.04 | ≤ 0.04 |
The processing parameter of table 2 pipe line steel
| Specimen coding | The continuous casting superheating temperature, ℃ | Pulling rate, m/min | Heating temperature, ℃ | Start rolling temperature, ℃ | Finishing temperature, ℃ | Speed of cooling, ℃/min |
| 1 | 15 | 0.70 | 1160 | 1150 | 920 | 0.6 |
| 2 | 20 | 0.68 | 1200 | 1180 | 950 | 0.7 |
| 3 | 25 | 0.65 | 1220 | 1190 | 960 | 0.9 |
Embodiment 2: the physical property of steel
According to resisting sulfide stress corrosion (anti-SSC) performance of NACE TM 0177-1996 (NACE of NACE standard) mensuration pipe line steel, measure CSR (the responsive rate of the crackle) index of the anti-HIC of pipe line steel according to NACE TM 0284-1996; Measurement result sees Table 3.
The physical property of table 3 steel
| Specimen coding | Resisting sulfide stress corrosion (anti-SSC) (stress=0.8 σ s) | Anti-HIC | Remarks |
| 1 | 96h does not split | CSR＝0.25 | |
| 2 | 96h does not split | CSR＝0.40 | |
| 3 | 96h does not split | CSR＝0.60 | |
| Compared steel | The 96h cracking | CSR＝1.65 |
As can be seen from Table 3, resisting sulfide stress corrosion of pipe line steel of the present invention (anti-SSC) and anti-HIC obviously are better than compared steel.
Claims (4)
1, the manufacture method of the seamless pipe line steel of a kind of microalloying, comprise smelting, refining, continuous casting, hot rolling, retarded cooling process step, the composition of the seamless pipe line steel of described microalloying percentage ratio by weight is: C:0.08～0.20%, Si :≤0.40%, Mn:0.60～1.50%, S≤0.015%, P≤0.025%, Al≤0.04%, Ti≤0.04%, H :≤2.5 * 10
-4%, O :≤25 * 10
-4%, surplus is Fe and unavoidable impurities;
It is characterized in that, smelt and alloying: electrosmelting, slag free tapping, adopt external refining, vacuum outgas to handle to chemical ingredients and meet the requirements, hydrogen richness is not more than 2.5 * 10 in the steel
-4%, oxygen level are not more than 25 * 10
-4%; Continuous casting, control superheating temperature superheating temperature are that 10～30 ℃, pulling rate are 0.50～0.85m/min; Hot rolling: strand is 1130～1280 ℃ in the Heating temperature of process furnace, 1100～1500 ℃ of start rolling temperatures, finishing temperature=850～980 ℃; Roll the back slow cooling, speed of cooling is 0.5～1 ℃/min.
2. the manufacture method of the seamless pipe line steel of microalloying as claimed in claim 1 is characterized in that, acid-soluble aluminum content is controlled between 0.010～0.030% in going into VD stokehold steel.
3, the manufacture method of the seamless pipe line steel of microalloying as claimed in claim 1 or 2; it is characterized in that; described refining is the LF+VD refining; adopt hypoxemia, low aluminium Refining Clean Steel in ASEA-SKF technology; the abundant pre-deoxidation of electric furnace steel tapping; LF adopts SiC and calcium-silicon compound deoxident diffusive deoxidation to keep white slag to replace hello aluminum steel deoxidation refining period, and argon shield is fully stirred down, by feeding CaSi line aluminate is carried out denaturing treatment.
4. the round steel made of the manufacture method of the seamless pipe line steel of the described microalloying of claim 1.
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