CN105925899A - Quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe and preparation method thereof - Google Patents

Quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe and preparation method thereof Download PDF

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CN105925899A
CN105925899A CN201610549035.XA CN201610549035A CN105925899A CN 105925899 A CN105925899 A CN 105925899A CN 201610549035 A CN201610549035 A CN 201610549035A CN 105925899 A CN105925899 A CN 105925899A
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line pipe
hydrogen sulfide
quenched
sulfide corrosion
steel
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CN105925899B (en
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邓叙燕
刘珂
李健强
李英真
冯莹
李玲霞
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DALIPAL PIPE Co
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium

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Abstract

The invention discloses a quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe and a preparation method thereof, and relates to the technical field of line pipe manufacturing. The quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe is prepared from, by weight percent, 0.11-0.14% of C, 0.15-0.35% of Si, 0.8-1.5% of Mn, 0.01-0.02% of Ti, 0.0015% or less of S, 0.01% or less of P, 0.015-0.030% of Al, 0.0015-0.0025% of Ca, 0.008% or less of N, 0.08% or less of Ni, 0.08% or less of Cu, 0.2% or less of Cr, 0.1% or less of Mo, 0.03% or less of V, 0.02% or less of Nb, 0.39% or less of CEQ, and the balance Fe and unavoidable impurities. The line pipe is simple in alloy component, low in cost, high in yield, excellent in mechanical performance and hydrogen sulfide corrosion resisting performance and capable of being widely applied to development of gas fields containing hydrogen sulfide.

Description

A kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe and preparation method thereof
Technical field
The present invention relates to the manufacturing technology field of line pipe.
Background technology
According to statistics, in the most explored oil gas field, about 1/3 contains hydrogen sulfide gas, as the oil gas field such as the Sichuan of China, long celebrating, Central Plains, North China, Tarim Basin all contains hydrogen sulfide gas in various degree.External also have many oil gas fields containing hydrogen sulfide gas, such as the Panamanian oil field of the U.S., your oil field, gulf of Canadian alberta truncation etc..If still using 20# carbon steel as gathering line in wet hydrogen sulfide environment, serious etching problem can be there is, there is great potential safety hazard, will result in huge economic loss.
Predicting according to internal authority mechanism, from 2000 ~ the year two thousand thirty, the demand of world oil increases by 1.6% every year, and the year two thousand thirty is up to 57.69 hundred million tons；The demand of natural gas increases by 2.4% every year, and the year two thousand thirty is up to 42.03 hundred million tons of oil equivalents.Along with the quick growth of oil and natural gas demand, the exploitation to the most hydrogen sulfide containing common Oil/gas Well can not meet demand, and the exploitation of sulfide hydrogen Oil/gas Well is increasing.Therefore, the consumption of the sulfur resistive line pipe being used for oil-gas gathering and transportation during exploitation of oil-gas field will increase considerably.Hydrogen sulfide corrosion resistant line pipe all has strict requirements to sulfur content, phosphorus content, the quantity of field trash and form, microstructure form and uniformity, comprehensive physicochemical property.Although compared with welded tube, there is not inborn HIC/SSC formation of crack in the shaping characteristic of seamless pipe, but owing to carbon content requires the lowest, there is following difficult point when producing sulfur resistive line pipe in the mode using seamless-molding: 1. steel is softer, godet easy steel bonding when using accurate Tube Rolling Train rolling, causes surface tear；2. the martensite content formed in quenching process is few, and quenching hardness is low, easily bends under the effect of quenching stress.Therefore, hydrogen sulfide corrosion resistant seamless line pipe added value of product is high, production process difficulty is relatively big, has become as a study hotspot of iron and steel enterprise the most both at home and abroad.
Steel industry comes into low margin age at present, domestic steel industry homogeneity competition, use the alloying component of minimizing, excellent material property is obtained by the effectively control of optimized production process flow process and production process, thus reduce production cost, also it is a Main way of present steel emtallurgy research.
Forefathers' property relationship to alloying element Yu steel has carried out relatively systematic research.
Carbon: carbon is most economical alloying element, intensified element, but the solderability of steel is affected the biggest by it.Therefore, over more than 20 year, the carbon content of pipe line steel is progressively to trend towards low-carbon (LC) or Ultra-low carbon direction is developed.And along with the increase of phosphorus content, toughness declines, segregation aggravation, the ability of hic resistance and SSC declines.Therefore, along with the raising of pipe line steel rank, carbon content should be gradually lowered.But phosphorus content can not be too low, because the reduction of carbon content, the intensity that not only can make steel reduces, and owing to carbon is to be present in steel with interstitial element, when carbon content is less than 0.01%, the bond strength of crystal boundary is extremely low, not only reduce the toughness of mother metal, make the crystal boundary of heat affected area in the most brittle state simultaneously.
Manganese: in steel, the reduction of carbon content can cause its yield strength to decline, it is possible to use other strengthening mechanisms are recompensed, most common of which is while fall C, with Mn for C.Manganese can play the effect of solution strengthening, also improves toughness improving intensity simultaneously, reduces the brittle transition temperature of steel.Manganese can also reduce phase transition temperature, makes ferritic crystal grain refine.But the too high meeting of Fe content causes the center segregation of pipe, the Properties of HIC resistance of steel pipe inner wall is caused to reduce.
Micro alloying element:
In low carbon manganese steel, addition niobium, vanadium, titanium these three micro alloying element are remarkably improved its intensity, and they mainly affect the performance of steel by crystal grain refinement and precipitation-hardening.
The niobium of trace is remarkably improved the recrystallization temperature of austenite, provides the temperature space more widened for non-recrystallization zone, it is possible to effectively stop the Recovery and recrystallization of deformed austeaite, the beneficially accumulation of ausforming amount.In high-temperature region, the migration of crystal boundary is played drag interaction by the niobium atom of solid solution；In low temperature austenitic area, Nb (C, the N) particle of strain induced precipitate serves the effect of pinning dislocation.
Vanadium is the main intensity improving steel with V (C, N) as the precipitation phase that low temperature separates out in acicular ferrite.
Solid solution nitrogen content in steel to be reduced, generally uses Trace Titanium Treatment, makes the nitrogen in steel be fixed by titanium.Owing to the solution temperature of TiN is much higher compared with the nitride of niobium or vanadium, it can more effectively stop austenite crystal to grow up to ensure that blank has thinner initial austenite crystal grain and prevents growing up of welding heat affected zone crystal grain in heating process, thus significantly improve the toughness of welding heat affected zone, improve the weldability of steel.
Other alloying elements:
Molybdenum can expand austenite phase field, postpones pro-eutectoid ferrite and the transformation of pearlite, reduces the phase transition temperature of overcooling austenite, the formation of suppression polygonal ferrite, promotes that acicular ferrite changes.Meanwhile, containing in Nb pipe line steel, Mo can improve the Nb (C, N) solid solubility in austenite, reduce the Precipitation Temperature of Nb (C, N), make more Nb (C, N) separate out in Low-temperature Iron ferritic, thus improve the precipitation strength effect of Nb (C, N).
In pipe line steel, add the alloying elements such as Cu, Ni, Cr, form passivating film on its surface, reduce the invasion of hydrogen, thus prevent the generation of hydrogen induced cracking.Can also effectively improve weather-resistance simultaneously.It addition, these elements also have the effect of strengthening matrix.
The composition of sulfur resistive line pipe is designed by each Steel Pipe Enterprise at present is all to add the elements such as Nb, V, Ti, Mo, Cu, Ni on the basis of C-Mn steel in a large number to improve its intensity and sulfur resistance.
In existing technology, there are Application No. 201010130911.8, invention entitled a kind of high intensity, anti-CO2And H2The Chinese patent of S corrosion seamless gathering-line pipe, its line pipe composition by weight percent is: C 0.01～0.1%, Si 0.1～0.5%, Mn 0.1～1%, P≤0.02%, S≤0.003%, Cr 1.0～7.0%, Mo 0.1～2%, Cu 0.1～0.5%, Ni 0.05～0.75%, Al 0.01～0.1%, Ni≤0.1%, V≤0.1%, Ti≤0.1%, rare earth element 0.01%～0.1%, remaining is Fe.After using electric arc furnaces or converter smelting to obtain circular pipe, using Mannesman roll seamless steel tube technique to make seamless hollow forging, hollow forging is conditioned or normalized treatment can be made into the anti-CO of X522And H2S corroded pipeline pipe.But in this technology, add the expensive alloying elements such as substantial amounts of Cu, Ni, Mo, relatively costly.Although adding nickel element in steel, it is possible to decrease steel hydrogen-absorption speed in acid condition, be conducive to improving the ability of hic resistance.But rare due to nickel, is again important strategic materials, non-when not reaching performance requirement with other alloying elements, it should the fewest with or without nickel as the alloying element of steel.Copper can form passivating film in sour environment, is also beneficial to slow down corrosion, but same copper is also belonging to the metal of costliness.
In existing technology, having Application No. 201210084138.5, the Chinese patent of the production method of the pipeline with hydrogen sulfide corrosion resistance seamless steel pipe of invention entitled a diameter of 508mm, its line pipe composition by weight percent is: C 0.08～0.12%, Si 0.20～0.35%, Mn 1.2～1.4%, Mo 0.01～0.15%, Al 0.01～0.05%, V 0.04～0.07%, Nb 0.02～0.04%, P≤0.01%, S≤0.002%, surplus is Fe and inevitable impurity.The raw material of configuration make pipe through electric furnace+LF stove+vacuum refining furnace+continuous casting flow process；Pipe obtains seamless line pipe after rolling and modifier treatment；The metallographic structure of body is tempering bainite and ferritic structure, and grain size is more than >=8.0 grades, and yield strength, at 380 more than MPa, meets the requirement of X52 sulfur resistive line pipe.But in this technology, add the expensive alloying elements such as substantial amounts of Nb, V, Mo, the most relatively costly.
In existing technology, having Application No. 201310398925.1, invention entitled a kind of X52 seamless line pipe with Properties of HIC resistance and the Chinese patent of manufacture method thereof, its line pipe composition by weight percent is: C 0.08～0.16%, Si 0.20～0.40%, Mn 1.0～1.6%, Ti 0.01～0.04%, V 0.03～0.08%, Cu 0.20～0.30%, Ni 0.15～0.25%, P≤0.015%, S≤0.010%, surplus is Fe and inevitable impurity.Process for making includes that converter smelting, external refining (LF), continuous casting, tandem rolling obtain pipe, heating of pipe blank, MPM tandem rolling, heat treatment.Its metallographic structure is tempered sorbite.But in this technology, add the expensive alloying elements such as substantial amounts of Cu, Ni, V, the most relatively costly.
As can be seen here, the design of alloy of sulfur resistive line pipe can have multiple choices, and improve alloying component and not only make the cost of steel increase, it is also possible to has a negative impact material property.Therefore, the production of sulfur resistive line pipe should seek optimal balance in design of alloy, preparation technology and the manufacture equipment being available for employing, reduces manufacturing cost to greatest extent under conditions of ensureing product combination property.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe and preparation method thereof, the alloying component system of this line pipe is simple, low cost of manufacture, lumber recovery is high, mechanical property and hydrogen sulfide corrosion resistance can be excellent, can be widely used for the exploitation of sulfide hydrogen oil gas field, wide market.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe, the chemical component weight percentage of line pipe is: 0.11%≤C≤0.14%, 0.15%≤Si≤0.35%, 0.8%≤Mn≤1.5%, 0.01%≤Ti≤0.02%, S≤0.0015%, P≤0.01%, 0.015%≤Al≤0.030%, 0.0015%≤Ca≤0.0025%, N≤0.008%, Ni≤0.08%, Cu≤0.08%, Cr≤0.2%, Mo≤0.1%, V≤0.03%, Nb≤0.02%, remaining is Fe and inevitable impurity, carbon equivalent ce Q≤0.39%；In line pipe, the percentage by weight of Fe content and the wall thickness of line pipe meet following relation: t/20+0.65≤100Mn≤t/20+0.75, and wherein, t is the wall thickness of line pipe, and the unit of t is mm；Mn is the percentage by weight of Fe content in line pipe；Smelting, refining, continuous casting, heat, bore a hole, roll, cool down, line pipe that heat treatment quenching and tempering prepares.
Line pipe hydrogen sulfide corrosion resistance can meet NACE TM0284-2011 and NACE TM0177-2005 standard specifies.
Preferably, heat treatment quenching and tempering be high-temperature heater is heated to 860 ~ 900 DEG C and is incubated after, in using first, after spray, the outer mode drenched carries out water-cooled；Then steel pipe is heated to 640 ~ 680 in low-temperature heat stove DEG C and be incubated, air cooling.
The thought of Design of Chemical Composition:
1. using titanium microalloying on the basis of C-Mn steel, nanoscale TiN or Ti (C, the N) particle separated out in solid phase will suppress Austenite Grain Growth in heating and course of hot rolling, thus improve toughness.The affinity of Ti Yu S is better than the affinity of Mn Yu S, forms Ti4C2S2, improve the sulfur resistance of steel.The ductile-brittle transition temperature of steel is raised to have and significantly affects by the free N in steel, molten steel is carried out Trace Titanium Treatment and can reduce the activity of the N in steel.The stoichiometric 3.4:1 of Ti and N in pure TiN.But Ti content is the highest, the formation temperature of TiN is higher, particle is relatively coarse, it is unfavorable for the plasticity of steel, and in view of there is Al, Mn, Cr and the impact of other nitride forming element reduction nitrogen activity in steel, the burden control of Ti and N in molten steel is proper 2.Due to the nitrogen content in steel generally at 0.005-0.08%, the Ti content of optimization is 0.01-0.02%.
2., when the molten Al content of the acid in steel is higher than 0.015%, thin austenite crystal can be obtained when reheating during welding and heat treatment, but austenite grain size is not affected by too high acid molten Al content.
3. for continuous cast round billets, the center segregation of phosphorus is probably in steel and adds 10 times or 20 times of phosphorus content.Therefore in sour environment, phosphorus content should be limited in less than 0.01%.
4. the sulphur in steel is easily combined with manganese, generates plasticity manganese sulfide inclusion, rolls after cure manganese and forms strip field trash, because there is line differences in expansion with body, cause being formed between manganese sulfide and body microgap, and hydrogen is easily assembled at microgap between manganese sulfide and body, form crackle along with hydrogen pressure increases.Therefore for sulfur resistive line pipe, if NACE to be passed through During A method inspection in TM0177-2005 standard, sulfur content is necessarily less than 0.0015% and Calcium treatment to be carried out.
5. in steel, calcium content is too high has the disadvantage that: 1) can reduce short-circuit frequency and will further decrease heat input, thus cause welding splash increase and the disappearance of sidewall fusion；2) show that the inclusion content in steel is higher, be unfavorable for being checked by HIC；3) easily corroding the mouth of a river in casting process and produce Large Inclusions, mold liquid level instability causes slag, is unfavorable for the cleanliness factor of molten steel.Therefore need not require higher calcium sulfur ratio in smelting process harshly, calcium content need to control below 0.0025%.
6. when using accurate oblique milling unit rolling seamless pipe, if the wall thickness of steel pipe is relatively thin, the cooling effect in the operation of rolling is preferable, and the crystal grain of rolling state is relatively thin, and intensity is higher.Therefore, Fe content is designed according to the wall thickness of steel pipe.
7. alloying component does not add the corrosion-resistant element such as Cu, Ni, does not add the intensified elements such as Nb, V, but can be compensated by the precise controlling degree of purity of steel, the uniformity of tissue, the manufacture process optimizing steel pipe.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe, comprises the steps:
1) smelting procedure: with steel scrap and the pig iron as raw material, make continuous cast round billets through arc melting, ladle refining, VD vacuum outgas, continuous casting working procedure；
2) tube rolling operation: obtain rolling state seamless steel pipe by the qualified continuous cast round billets obtained by step 1) after annular furnace heating, perforation, accurate oblique milling unit rolling, micro-tension reducing, walking beam cooler cooling；
3) heat treatment quenching and tempering operation: by step 2) steel pipe that obtains is heated to 860 ~ 900 in high temperature furnace DEG C and after being incubated, in using first, after spray, the outer mode drenched carries out water-cooled；Then steel pipe is heated to 640 ~ 680 in tempering heating furnace DEG C and be incubated, after air cooling, obtain quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe.
Preferably, in the arc melting operation in step 1), during arc furnace tapping, add 1.5 ~ 2.5 Kg/t aluminium ingot, 8 ~ 9 kg/t manganese metals, 1.5 ~ 2.5 Kg/t FeSi carries out deoxidation alloying；Add 4.5 ~ 5.5 kg/t pro-molten refining slags, 7 ~ 9 kg/t lime carry out slag making preliminary refining in advance；Carbon content≤0.05 in manganese metal Wt.%, phosphorus content≤0.03 wt.%.
Preferably, in the arc melting operation in step 1), when in molten bath, carbon content is 0.06-0.09 Wt.%, phosphorus content≤0.008 wt.%, temperature are 1600-1630 DEG C time tapping.
Preferably, in the VD vacuum outgas operation in step 1), ladle uses the operation of soft blow argon, it is ensured that molten steel is exposed；Molten steel processes 15 min under the conditions of the Pa of vacuum≤67；VD breaks in empty backward molten steel feeding silicon-calcium wire, then hangs ladle toward continuous casting platform after carrying out the soft blow argon stirring of 15 min.
Preferably, step 2) in accurate oblique milling unit rolling process in, use and concentrate deformation roll, deformation section length≤30 mm of roll.
Preferably, step 2) in walking beam cooler refrigerating work procedure in, it is 870 ~ 890 DEG C that line pipe enters cold bed temperature, uses blower fan and water smoke cooling after entering cold bed, and after line pipe crosses blower fan, temperature is 400 ~ 500 DEG C, and it is 200 ~ 300 DEG C that line pipe goes out cold bed temperature.
Preferably, in step 3), the outer pouring time controls to control at 11 s in 13 s, interior spray time, and the outer pouring time started is than interior spray time started late 1 s.
API Specifying in Spec 5L the 45th edition that X52 level hydrogen sulfide corrosion resistant seamless line pipe can be delivered goods with normalized condition or quality adjustment condition (quenching+high tempering), ferrite+pearlitic structrure that the tempered sorbite that hardening and tempering process obtains organizes relatively normalizing process to obtain has more preferable hydrogen sulfide corrosion resistance energy.
Use and have the beneficial effects that produced by technique scheme:
1) present tube spool chemical composition system is simple, without valuable alloying element, makes up, by improving the cleanliness factor of molten steel, the corrosion resistance loss of energy that alloy decrement is caused.
2) smelting process uses manganese metal to carry out alloying, carbon and phosphorus content in manganese metal are low, carbon content and the phosphorus content of arc furnace tapping can be improved, this consumption that not only can save arc melting process lime and power consumption, significantly reduce the consumption of iron and steel stock, and the melting task of electric arc furnaces can be alleviated, shorten smelting cycle, it is advantageously implemented converter-CCM matching, it is achieved sequence casting.
3) operation of rolling uses and concentrates deformation roll, increases the gap between godet and steel pipe, reduces the frictional force of godet, thus solves the problem of godet steel bonding, is conducive to improving surface quality and the lumber recovery of steel pipe.
4) problem that in quenching process uses first, after spray, the outer mode drenched is easily bent after solving steel pipe quenching.
5) the line pipe alloy content of the present invention is low, and manufacture process is simple, lumber recovery is high, and can save the manufacturing cost of more than 10%, mechanical property and hydrogen sulfide corrosion resistance can be excellent, can be widely used for the exploitation of sulfide hydrogen oil gas field, wide market.
Accompanying drawing explanation
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings；
Fig. 1 is the X52 hydrogen sulfide corrosion resistant seamless line pipe yield strength distribution figure obtained by embodiment of the present invention 1-3；
Fig. 2 is the X52 hydrogen sulfide corrosion resistant seamless line pipe tensile strength distribution map obtained by embodiment of the present invention 1-3；
Fig. 3 is the elongation percentage distribution map of the X52 hydrogen sulfide corrosion resistant seamless line pipe obtained by embodiment of the present invention 1-3；
Fig. 4 is-80 DEG C of ballistic work distribution maps of the X52 hydrogen sulfide corrosion resistant seamless line pipe obtained by embodiment of the present invention 1-3.
Detailed description of the invention
Embodiment 1
With steel scrap and the pig iron as raw material, making the continuous cast round billets of a diameter of Φ 160 mm through 80t arc melting, ladle refining, VD vacuum outgas, continuous casting working procedure, the percentage by weight of its chemical composition is: C 0.11%、Si 0.28%、Mn 1.0%、S 0.0011%、P 0.008%、Ti 0.012%、Al 0.025%、Ca 0.002%、N 0.007%、Ni 0.03%、Cu 0.04%, Cr 0.05%, remaining is Fe and inevitable impurity.
Electric arc furnace smelting operation uses arc heat molten pig iron and steel scrap and makes molten bath heat up, coherent oxygen lance is used to carry out oxygen decarburization and intensification, add 3t active lime and carry out slag making, dephosphorization, when in molten bath, carbon content is 0.06-0.09 wt.%, phosphorus content≤0.008wt.%, temperature can tap when being 1600-1630 DEG C.1.5 ~ 2.5 kg/t aluminium ingots, 8 ~ 9 kg/t manganese metals, 1.5 ~ 2.5 kg/t are added during arc furnace tapping FeSi carries out deoxidation alloying；Add 4.5 ~ 5.5 kg/t pro-molten refining slags, 7 ~ 9 kg/t lime carry out slag making preliminary refining in advance；Carbon content≤0.05 in manganese metal Wt.%, phosphorus content≤0.03 wt.%.
In ladle refining operation, after ladle arrives at a station, energising heats up, and refining process adds lime, fluorite and calcium carbide slag making, desulfurization, the alloying component of fine setting molten steel.
In VD vacuum outgas operation, ladle uses the operation of soft blow argon, it is ensured that molten steel is exposed；Molten steel processes 15 min under the conditions of the Pa of vacuum≤67；VD breaks and adds 30 kg ferrotianiums in empty backward molten steel, then feeds 250 m silicon-calcium wires, then hangs ladle toward continuous casting platform after carrying out the soft blow argon stirring of 15 min.
In round billet continuous casting operation, casting process uses whole process protection casting, and tundish uses high alkalinity coverture and carbonization rice husk double shielding, and logic approach for mold level control is within ± 3 mm, and the crystallizer of conticaster and solidification end all use electromagnetic agitation.
Continuous cast round billets heats through annular furnace, perforation, accurate oblique milling unit rolling, micro-tension reducing, walking beam cooler cool down, after quenching+tempering modifier treatment, make external diameter be 114.3 mm, wall thickness be 5.9 The quenched and tempered state seamless line pipe of mm；
In annular furnace heating process, the temperature of bringing-up section is 1240～1280 DEG C, and the temperature of soaking zone is 1240～1260 DEG C, and the tapping temperature of pipe is 1120～1140 DEG C；Furnace temperature uses fully-automatic intelligent closed-loop control system, and furnace gas temperature control accuracy is up to ± 10 DEG C.
In perforation process, the Novel tapered two-roll piercer using roll off angle to be 12 °, the preperforative temperature of pipe is 1050～1060 DEG C, and the temperature after pipe perforation is 1140～1150 DEG C；
In accurate oblique milling unit rolling process, roll off angle is 12 °, and the temperature before pipe hot rolling is 1040～1050 DEG C；
In micro-tension reducing operation, reducing rate≤2.5% of single chassis；
In walking beam cooler cooling, it is 870～890 DEG C that line pipe enters cold bed temperature, uses blower fan and water smoke cooling after entering cold bed, and after line pipe crosses blower fan, temperature is 400～500 DEG C, and it is 200～300 DEG C that line pipe goes out cold bed temperature.
In quenched operation, steel pipe is heated to 860 ~ 900 DEG C in high-temperature heater and is incubated 10 After min, in using first, after spray, the outer mode drenched carries out water-cooled, and the outer pouring time controls at 13 s, water rate control at 2500 m3/ h, the interior spray time controls at 11 s, water rate control at 400 m3/ h, the outer pouring time started is than interior spray time started late 1 s；Then steel pipe is heated in low-temperature heat stove 640 ~ 680 DEG C and is incubated 25 Min, obtains quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe after air cooling.
Embodiment 2
With steel scrap and the pig iron as raw material, making the continuous cast round billets of a diameter of Φ 180 mm through 80t arc melting, ladle refining, VD vacuum outgas, continuous casting working procedure, the percentage by weight of its chemical composition is: C 0.12%、Si 0.23%、Mn 1.1%、S 0.0012%、P 0.007%、Ti 0.015%、Al 0.024%、Ca 0.0018%、N 0.007%、Ni 0.03%、Cu 0.04%, Cr 0.05%, remaining is Fe and inevitable impurity.
Electric arc furnace smelting operation uses arc heat molten pig iron and steel scrap and makes molten bath heat up, coherent oxygen lance is used to carry out oxygen decarburization and intensification, add 3t active lime carry out slag making, dephosphorization, when in molten bath carbon content be 0.06-0.09 wt.%, phosphorus content≤0.008 wt.%, temperature be 1600-1630 DEG C time can tap.1.5 ~ 2.5 kg/t aluminium ingots, 8 ~ 9 kg/t manganese metals, 1.5 ~ 2.5 kg/t are added during arc furnace tapping FeSi carries out deoxidation alloying；Add 4.5 ~ 5.5 kg/t pro-molten refining slags, 7 ~ 9 kg/t lime carry out slag making preliminary refining in advance；Carbon content≤0.05 in manganese metal Wt.%, phosphorus content≤0.03 wt.%.
In ladle refining operation, after ladle arrives at a station, energising heats up, and refining process adds lime, fluorite and calcium carbide slag making, desulfurization, the alloying component of fine setting molten steel.
In VD vacuum outgas operation, ladle uses the operation of soft blow argon, it is ensured that molten steel is exposed；Molten steel processes 15 min under the conditions of the Pa of vacuum≤67；VD breaks and adds 30 kg ferrotianiums in empty backward molten steel, then feeds 250 m silicon-calcium wires, then hangs ladle toward continuous casting platform after carrying out the soft blow argon stirring of 15 min.
In round billet continuous casting operation, casting process uses whole process protection casting, and tundish uses high alkalinity coverture and carbonization rice husk double shielding, and logic approach for mold level control is within ± 3 mm, and the crystallizer of conticaster and solidification end all use electromagnetic agitation.
Continuous cast round billets heats through annular furnace, perforation, accurate oblique milling unit rolling, micro-tension reducing, walking beam cooler cool down, after quenching+tempering modifier treatment, make external diameter be 168.3 mm, wall thickness be 7.11 The quenched and tempered state seamless line pipe of mm；
In annular furnace heating process, the temperature of bringing-up section is 1240～1280 DEG C, and the temperature of soaking zone is 1240～1260 DEG C, and the tapping temperature of pipe is 1120～1140 DEG C；Furnace temperature uses fully-automatic intelligent closed-loop control system, and furnace gas temperature control accuracy is up to ± 10 DEG C.
In perforation process, the Novel tapered two-roll piercer using roll off angle to be 12 °, the preperforative temperature of pipe is 1050～1060 DEG C, and the temperature after pipe perforation is 1140 ~ 1150 DEG C；
In accurate oblique milling unit rolling process, roll off angle is 12 °, and the temperature before pipe hot rolling is 1040～1050 DEG C；
In micro-tension reducing operation, reducing rate≤2.5% of single chassis；
In walking beam cooler cooling, it is 870 ~ 890 DEG C that line pipe enters cold bed temperature, uses blower fan and water smoke cooling after entering cold bed, and after line pipe crosses blower fan, temperature is 400 ~ 500 DEG C, and it is 200 ~ 300 DEG C that line pipe goes out cold bed temperature.
In quenched operation, steel pipe is heated to 860 ~ 900 DEG C in high-temperature heater and is incubated 11 After min, in using first, after spray, the outer mode drenched carries out water-cooled, and the outer pouring time controls to control at 11 s in 13 s, interior spray time, and the outer pouring time started is than interior spray time started late 1 s；Then steel pipe is heated to 640 ~ 680 DEG C and is incubated 30 in tempering heating furnace Min, obtains quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe after air cooling.
Embodiment 3
With steel scrap and the pig iron as raw material, making the continuous cast round billets of a diameter of Φ 210 mm through 80t arc melting, ladle refining, VD vacuum outgas, continuous casting working procedure, the percentage by weight of its chemical composition is: C 0.13%、Si 0.25%、Mn 1.2%、S 0.0011%、P 0.007%、Ti 0.013%、Al 0.026%、Ca 0.0021%、N 0.007%、Ni 0.03%、Cu 0.04%, Cr 0.05%, remaining is Fe and inevitable impurity.
Electric arc furnace smelting operation uses arc heat molten pig iron and steel scrap and makes molten bath heat up, coherent oxygen lance is used to carry out oxygen decarburization and intensification, add 3t active lime and carry out slag making, dephosphorization, when in molten bath, carbon content is 0.06-0.09 wt.%, phosphorus content≤0.008wt.%, temperature can tap when being 1600-1630 DEG C.1.5 ~ 2.5 kg/t aluminium ingots, 8 ~ 9 kg/t manganese metals, 1.5 ~ 2.5 kg/t are added during arc furnace tapping FeSi carries out deoxidation alloying；Add 4.5 ~ 5.5 kg/t pro-molten refining slags, 7 ~ 9 kg/t lime carry out slag making preliminary refining in advance；Carbon content≤0.05 in manganese metal Wt.%, phosphorus content≤0.03 wt.%.
In ladle refining operation, after ladle arrives at a station, energising heats up, and refining process adds lime, fluorite and calcium carbide slag making, desulfurization, the alloying component of fine setting molten steel.
In VD vacuum outgas operation, ladle uses the operation of soft blow argon, it is ensured that molten steel is exposed；Molten steel processes 15 min under the conditions of the Pa of vacuum≤67；VD breaks and adds 30 kg ferrotianiums in empty backward molten steel, then feeds 250 m silicon-calcium wires, then hangs ladle toward continuous casting platform after carrying out the soft blow argon stirring of 15 min.
In round billet continuous casting operation, casting process uses whole process protection casting, and tundish uses high alkalinity coverture and carbonization rice husk double shielding, and logic approach for mold level control is within ± 3 mm, and the crystallizer of conticaster and solidification end all use electromagnetic agitation.
Continuous cast round billets heats through annular furnace, perforation, accurate oblique milling unit rolling, micro-tension reducing, walking beam cooler cool down, after quenching+tempering modifier treatment, make external diameter be 219.1 mm, wall thickness be 9.5 The quenched and tempered state seamless line pipe of mm；
In annular furnace heating process, the temperature of bringing-up section is 1240～1280 DEG C, and the temperature of soaking zone is 1240～1260 DEG C, and the tapping temperature of pipe is 1120～1140 DEG C；Furnace temperature uses fully-automatic intelligent closed-loop control system, and furnace gas temperature control accuracy is up to ± 10 DEG C.
In perforation process, the Novel tapered two-roll piercer using roll off angle to be 12 °, the preperforative temperature of pipe is 1050～1060 DEG C, and the temperature after pipe perforation is 1140～1150 DEG C；
In accurate oblique milling unit rolling process, roll off angle is 12 °, and the temperature before pipe hot rolling is 1040～1050 DEG C；
In micro-tension reducing operation, reducing rate≤2.5% of single chassis；
In walking beam cooler cooling, it is 870～890 DEG C that line pipe enters cold bed temperature, uses blower fan and water smoke cooling after entering cold bed, and after line pipe crosses blower fan, temperature is 400～500 DEG C, and it is 200～300 DEG C that line pipe goes out cold bed temperature.
In quenched operation, steel pipe is heated to 860 ~ 900 DEG C in high-temperature heater and is incubated 15 After min, in using first, after spray, the outer mode drenched carries out water-cooled, and the outer pouring time controls to control at 11 s in 13 s, interior spray time, and the outer pouring time started is than interior spray time started late 1 s；Then steel pipe is heated in low-temperature heat stove 640 ~ 680 DEG C and is incubated 38 Min, obtains quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe after air cooling.
According to requirement its yield strength of sample analysis, tensile strength, elongation percentage, side knock merit from the seamless line pipe that embodiment 1～embodiment 3 prepare of API Spec 5L the 45th edition, its statistic analysis result is the most as shown in Figure 1 to 4.The number of the seamless line pipe by being taken of the sample number in figure.The yield strength of seamless line pipe prepared by above method is 400 ~ 494 MPa, tensile strength are 504 ~ 580 MPa, elongation percentage >=25% ,-80 DEG C of horizontal full-scale Xia Shi ballistic work >=200 J, ductil-brittle transition temperature≤-80 DEG C, wherein yield strength mean value be 440.1 MPa, standard deviation be 13.4 MPa, tensile strength mean value is 532.0 MPa, standard deviation is 13.1 MPa, elongation percentage mean value is 35.4%, standard deviation is 2.1%, and-80 DEG C of horizontal full-scale Xia Shi ballistic work mean value is 231.9 J, standard deviation is 16.4 J.
According to examination criteria NACE TM0284-2011(pipeline, the test method of pressure vessel Resistant hydrogen introduced cracking steel performance evaluation) sample in embodiment 1 ~ 3 has been carried out HIC performance evaluation, sample is at standard solution A (normal temperature and pressure, sodium chloride acetum containing saturated hydrogen sulfide) in after 96h, all of specimen surface is without hydrogen blister, and maximum average crack length rate CLR, maximum average crack thickness rate CTR, maximum average crack rate CSR are 0.According to examination criteria NACE TM0177-2005(hydrogen sulfide corrosion resistant split test) in A method the sample in embodiment 1 ~ 3 has been carried out SSC benchmark test, loading stress is 324 MPa(360 MPa × 90%), after 720h tests, sample all ruptures；10 times are amplified Microscopic observation specimen surface and are not found to be perpendicular to the crackle in specimen surface tension direction.
As can be seen here, the alloying component system of the X52 hydrogen sulfide corrosion resistant seamless line pipe prepared by said method is simple, low cost of manufacture, mechanical property and hydrogen sulfide corrosion resistance can be excellent, can be widely used for the exploitation of sulfide hydrogen Oil/gas Well, there are wide market prospects.
Principle and the embodiment of the present invention are set forth by specific case used herein, and the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and modification, these improve and modify the protection domain also falling into the claims in the present invention.

Claims (10)

1. a quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe, it is characterized in that, the chemical component weight percentage of described line pipe is: 0.11%≤C≤0.14%, 0.15%≤Si≤0.35%, 0.8%≤Mn≤1.5%, 0.01%≤Ti≤0.02%, S≤0.0015%, P≤0.01%, 0.015%≤Al≤0.030%, 0.0015%≤Ca≤0.0025%, N≤0.008%, Ni≤0.08%, Cu≤0.08%, Cr≤0.2%, Mo≤0.1%, V≤0.03%, Nb≤0.02%, remaining be Fe and inevitably impurity, carbon equivalent ce Q≤0.39%；In line pipe, the percentage by weight of Fe content and the wall thickness of line pipe meet following relation: t/20+0.65≤100Mn≤t/20+0.75, and wherein, t is the wall thickness of line pipe, the unit of t be mm, Mn be the percentage by weight of Fe content in line pipe；Smelting, refining, continuous casting, heat, bore a hole, roll, cool down, line pipe that heat treatment quenching and tempering prepares.
A kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 1, it is characterised in that: described line pipe hydrogen sulfide corrosion resistance can meet NACE TM0284-2011 and NACE TM0177-2005 standard specifies.
A kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 1, it is characterised in that heat treatment quenching and tempering is to be heated to 860 ~ 900 in high-temperature heater DEG C and after being incubated, in using first, after spray, the outer mode drenched carries out water-cooled；Then steel pipe is heated in low-temperature heat stove 640 ~ 680 DEG C and is incubated, air cooling.
4. the preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe as described in any one of claim 1-3, it is characterised in that comprise the steps:
1) smelting procedure: with steel scrap and the pig iron as raw material, make continuous cast round billets through arc melting, ladle refining, VD vacuum outgas, continuous casting working procedure；
2) tube rolling operation: obtain rolling state seamless steel pipe by the qualified continuous cast round billets obtained by step 1) after annular furnace heating, perforation, accurate oblique milling unit rolling, micro-tension reducing, walking beam cooler cooling；
3) heat treatment quenching and tempering operation: by step 2) after the steel pipe that obtains is heated to 860 ~ 900 DEG C in high-temperature heater and is incubated, in using first, after spray, the outer mode drenched carries out water-cooled；Then steel pipe it is heated in low-temperature heat stove 640 ~ 680 DEG C and is incubated, after air cooling, obtaining quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterized in that: in the arc melting operation in step 1), during arc furnace tapping, addition 1.5 ~ 2.5 kg/t aluminium ingots, 8 ~ 9 kg/t manganese metals, 1.5 ~ 2.5 kg/t FeSi carry out deoxidation alloying；Add 4.5 ~ 5.5 kg/t pro-molten refining slags, 7 ~ 9 kg/t lime carry out slag making preliminary refining in advance；Carbon content≤0.05 wt.% in manganese metal, phosphorus content≤0.03 wt.%.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterized in that: in the arc melting operation in step 1), when in molten bath carbon content be 0.06-0.09 wt.%, phosphorus content≤0.008 wt.%, temperature be 1600-1630 DEG C time tapping.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterised in that: in the VD vacuum outgas operation in step 1), ladle uses the operation of soft blow argon, it is ensured that molten steel is exposed；Molten steel processes 15 min under the conditions of the Pa of vacuum≤67；VD breaks in empty backward molten steel feeding silicon-calcium wire, then hangs ladle toward continuous casting platform after carrying out the soft blow argon stirring of 15 min.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterised in that: step 2) in accurate oblique milling unit rolling process in, use concentrate deformation roll, deformation section length≤30 of roll mm。
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterized in that: step 2) in walking beam cooler refrigerating work procedure in, it is 870 ~ 890 DEG C that line pipe enters cold bed temperature, blower fan and water smoke cooling is used after entering cold bed, after line pipe crosses blower fan, temperature is 400 ~ 500 DEG C, and it is 200 ~ 300 DEG C that line pipe goes out cold bed temperature.
The preparation method of a kind of quenched and tempered state X52 hydrogen sulfide corrosion resistant seamless line pipe the most according to claim 4, it is characterized in that: in step 3), the outer pouring time controls to control at 11 s in 13 s, interior spray time, and the outer pouring time started is than interior spray time started late 1 s.
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CN111926253B (en) * 2020-07-31 2021-10-22 五矿营口中板有限责任公司 Hydrogen sulfide corrosion resistant high-strength toughness normalized steel and manufacturing method thereof
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CN112359276A (en) * 2020-10-15 2021-02-12 中天钢铁集团有限公司 Low-cost moisture-resistant hydrogen sulfide corrosion-resistant steel, and preparation method and application thereof

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