CN104928602A - Pipeline steel, wide and thick plate, resistant to H2S corrosion, and production method thereof - Google Patents

Pipeline steel, wide and thick plate, resistant to H2S corrosion, and production method thereof Download PDF

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Publication number
CN104928602A
CN104928602A CN201510354276.4A CN201510354276A CN104928602A CN 104928602 A CN104928602 A CN 104928602A CN 201510354276 A CN201510354276 A CN 201510354276A CN 104928602 A CN104928602 A CN 104928602A
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corrosion
steel
production method
temperature
wide
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陆春洁
曲锦波
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Jiangsu Shagang Iron and Steel Research Institute Co Ltd
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Jiangsu Shagang Iron and Steel Research Institute Co Ltd
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Abstract

The invention relates to a pipeline steel, wide and thick plate, resistant to H2S corrosion, and a production method thereof. The pipeline steel, wide and thick plate comprises, by weight, 0.018% to 0.068% of C, 0.12% to 0.42% of Si, 0.33% to 0.68% of Mn, not greater than 0.0098% of P, not greater than 0.0098% of S, 0.022% to 0.062% of Nb, 0.009% to 0.021% of Ti, 0.28% to 0.67% of Cr, not greater than 0.32% of Ni, not greater than 0.47% of Cu, 0.013% to 0.057% of Alt, 0.001% to 0.05% of Sn, 0.001% to 0.05% of Sb, one or both of 0.001% to 0.05% of Sn and 0.001% to 0.05% of Sb, and the balance of iron and avoidable foreign. The production method includes the steps of smelting by a blast furnace, pretreatment of molten iron, processing by a converter, refining, vacuum degassing, continuous casting, slab heating, descaling, controlled rolling, controlled cooling and air cooling; heating for hot rolling is at 1150 to 1210 DEG C, final rolling temperature is 800 to 850 DEG C, and final cooling temperature is 450 to 600 DEG C. The low-Mn component design is adopted, Sn or/and Sb are added, no noble metals such as Mo are added, and smelting cost and alloy cost are lowered; by component design and process control, the produced pipeline steel, wide and thick plate, resistant to H2S corrosion, has good comprehensive performances.

Description

A kind of resistance to H 2the pipe line steel Wide and Thick Slab of S corrosion and production method thereof
Technical field
The present invention relates to metal material field, particularly the resistance to H of one 2the pipe line steel Wide and Thick Slab of S corrosion and production technique thereof.
Background technology
At oil, Sweet natural gas production field, along with the exhaustion of the low shallow well hydrocarbon resources of corrodibility, increasing the exploitation of the high high pressure and deep well of corrodibility, this kind of Oil/gas Well contains various corrosive gases, as H always 2s, CO 2deng, wherein H 2s corrosion be in oil-gas field corrosion the most seriously, the most dangerous one, very serious corrosion can be produced to the oil gas well casing in recovery process and the steel for pipe in transportation.
Hydrogen sulfide corrosion refers to the galvanic corrosion that steel occur in moisture hydrogen sulfide, comprise hydrogen blistering (HB), hydrogen induced cracking (HIC) (HIC), sulfide-stress cracking (SSCC) and hydrogen cracking by stress (SOHIC) etc., and wherein HIC and SSCC is modal two kinds of forms of corrosions in pipe line steel.It produces and all relates to the diffusion of hydrogen atom, gathering and hydrogen atom to the transformation of hydrogen molecule, by hindering the carrying out of these processes, all can improve the hydrogen sulfide corrosion resistance energy of pipe line steel.Existing hydrogen sulfide corrosion resistant technology comprises: improve the resistance of steel to hydrogen embrittlement by high purification, reduction segregation, control tissue etc.; Improving solidity to corrosion by adding the elements such as Ni, Cu, add corrosion inhibitor or implement aluminum coated steel etc. prevents hydrogen from invading in steel.
Patent documentation CN 1142309C discloses a kind of Ultra-low carbon high tenacity anti-H 2 S steel for gas delivering pipeline, the object of hydrogen sulfide corrosion resistant is reached by ultra-pure purification and organizational controls, wherein very low (the S < 0.0007% of S, P content requirement, P < 0.003%), add steel-making cost and difficulty; Patent documentation CN 100359035C discloses X 65 pipeline steel for use in acid condition and manufacture method thereof, and its pipe line steel is hot-rolled coil, and with the addition of the Mo of 0.05-0.195%, cost of alloy is high, and only possesses Properties of HIC resistance; Patent documentation CN 103627974A discloses a kind of production method improving the anti-hydrogen induced cracking of steel plate, with the addition of the Cr of 3.0-6.0%, reduce the addition of the precious alloys such as Ni, Mo, but the erosion resistance of Cr element to steel plate exists unkehr effect, and this steel only possesses Properties of HIC resistance.In existing hydrogen sulfide corrosion resistant technology, comparatively strict to S content requirement, steel-making difficulty and cost larger; The bullion contents such as Ni, Mo are high, and cost of alloy is higher; Solidity to corrosion usually improves in a large amount of use Cr unit, but more and more studies proof, and the erosion resistance of Cr element to steel plate exists unkehr effect.
Summary of the invention
For the deficiency that prior art exists, the object of the present invention is to provide a kind of resistance to H 2s corroded pipeline steel Wide and Thick Slab and production method thereof, adopt low Mn Composition Design, adds Sn or/and Sb, by Composition Design and technology controlling and process, produces hic resistance and all excellent pipe line steel Wide and Thick Slab of anti-SSCC performance.
For achieving the above object, the present invention adopts following technical scheme:
A kind of resistance to H 2the pipe line steel Wide and Thick Slab of S corrosion, its chemical composition composition is C:0.018-0.068% by mass percentage, Si:0.12-0.42%, Mn:0.33-0.68%, P :≤0.0098%, S :≤0.0098%, Nb:0.022-0.062%, Ti:0.009-0.021%, Cr:0.28-0.67%, Ni :≤0.32%, Cu :≤0.47%, Alt:0.013-0.057%, also comprise Sn:0.001-0.05%, one in Sb:0.001-0.05% or two kinds, all the other are iron and inevitable impurity.
In the present invention, the Main Function of each chemical composition is as follows:
Carbon (C): carbon is strengthening element most economical, the most basic in steel is easy segregation and carbide forming element, has negative impact to the ductility of steel, toughness, weldability and resistance to acid.During carbon content > 0.068%, cause Mn, P segregation to aggravate, make welding zone hardness increase, easy generation SSCC, but during carbon content < 0.018%, the yield tensile ratio of steel plate increases, therefore, the carbon content that the present invention selects is 0.018-0.068%.
Silicon (Si): requisite deoxidant element, has solution strengthening effect, during too high levels, to toughness and weldability unfavorable, therefore, the present invention select Si content be 0.12-0.42%.
Manganese (Mn): solution strengthening element, easily generate MnS and be mingled with, and the plasticity that MnS is mingled with increases along with Mn concentration and increases, and MnS to be mingled be the one of the main reasons causing hydrogen induced cracking; Easy segregation, segregation place easily forms the sclerotic tissue that may become HIC producing cause; Pearlitic formation can be promoted, unfavorable to hydrogen sulfide corrosion-resistant performance.The present invention adopts low Mn Composition Design, can relax the requirement to S content in right amount, reduces smelting cost and difficulty, but when Mn content is too low, need add other alloying elements a large amount of to make up loss of strength, be unfavorable for cost control, therefore, Mn content is 0.33-0.68%.
Phosphorus (P): be inevitable impurity element in steel, promotes center segregation, and generate the ferrite-pearlite banded structure of P segregation, Properties of HIC resistance is deteriorated, and therefore, P content is≤0.0098%.
Sulphur (S): be inevitable impurity element in steel, easily form MnS and be mingled with, make hic resistance and SSCC degradation, therefore S content is≤0.0098%.
Niobium (Nb): be one of topmost strengthening element in pipe line steel, fairly obvious to Grain Refinement Effect, there is moderate precipitation strength.During too high levels, the recrystallization temperature of steel can be made to raise, be unfavorable for the refinement of former crystal grain difficult to understand, therefore, the Nb content that the present invention selects is 0.022-0.062%.
Titanium (Ti): strong N element, during with Nb acting in conjunction, contribute to improving the solid solubility of Nb in austenite, compound is separated out and is improved (TiNb) (CN) thermostability, Austenite Grain Growth when can effectively hinder slab to reheat, has obvious effect to the impelling strength improving welded heat affecting zone simultaneously.When adding excessive, form TiC more, TiN particle is thick, reduces the hardening capacity of steel, intensity and fatigue strength, reduces the high-temp plastic of steel in austenitic area, makes strand or stocking occur crackle.Therefore, the Ti content that the present invention selects is 0.009-0.021%.
Chromium (Cr): solution strengthening element, when steel is in carbonic acid gas and hydrogen sulfide corrosion environment, Cr element can at the surface enrichment of steel, form the amorphous microstructure of compact structure, improve the anti-local corrosion of pipe line steel and average corrosive power, during excessive interpolation, easily form more low-temperature phase and multiple containing Cr carbide in steel, reduce the toughness of toughness, weldability and welding zone.Therefore, the Cr content that the present invention selects is 0.28-0.67%.
Nickel (Ni): solution strengthening element, improve the red brittleness that Cu causes in steel, and it is useful to toughness, the solidity to corrosion of steel in hydrogen-sulfide environmental can be improved, too high levels, cost of alloy is increased, and can martensite transformation temperature be reduced, increase the ratio of twin crystal martensite and be unfavorable for the toughness of steel.Therefore, the Ni content that the present invention selects is≤0.32%.
Copper (Cu): improve steel plate and welded heat affecting zone intensity by solution strengthening, the anti-fatigue performance of steel is improved by precipitating action, promote that steel surface forms passive film, reduce the intrusion of protium, the effect of S in steel can also be offset, be combined the sulfide forming indissoluble with S, weaken the infringement of S to steel erosion resistance.Adding excessive meeting makes the weldability of steel be deteriorated, and at high temperature reduces melting grain-boundary strength and easily cracks when hot rolling.Therefore, the Cu content that the present invention selects is≤0.47%.
Aluminium (Al): the bioelement being steel-deoxidizing, forms the infusible compound AlN of small and dispersed distribution, crystal grain thinning in steel, improves the grain coarsening temperature of steel, also has oxidation-resistance and corrosion resistance.Excessive interpolation can reduce purity and the toughness of steel, and the castability of molten steel is declined, and affects the hot workability of steel, welding property and machinability.Therefore, the Al content that the present invention selects is 0.013-0.057%.
Tin (Sn): promote the densification containing Cu, Ni rusty scale, with Cr compound action, the acid fastness of rusty scale is improved, hinders H atom to enter steel matrix, suppresses the carrying out of corrosion.Can obtain above effect during content >=0.001%, during more than 0.01%, the hot workability of steel and toughness reduce, and therefore, the Sn content that the present invention selects is 0.001-0.05%.
Antimony (Sb): effect is identical with Sn, the Sb content that the present invention selects is 0.001-0.05%.
Resistance to H provided by the invention 2the production method of S corroded pipeline steel Wide and Thick Slab, production technique comprises: blast furnace ironmaking → hot metal pretreatment → converter steelmaking → refining → vacuum outgas → continuous casting → heating of plate blank → de-scaling → controlled rolling → control cold → air cooling.Wherein, treat that temperature thickness is 3-5 times of finished product thickness, entrance finishing temperature≤960 DEG C, finishing temperature is 800-850 DEG C, and final cooling temperature is 450-600 DEG C.
Further, described resistance to H 2in the production method of S corroded pipeline steel Wide and Thick Slab, hot rolling Heating temperature is 1150-1210 DEG C, and roughing temperature is 980-1080 DEG C, and rate of cooling is 20-30 DEG C/s.
Be polygonal ferrite and corynebacterium grain shellfish tissue by the organization type of the steel plate of above-mentioned explained hereafter.
The present invention compared with prior art, has following beneficial effect:
(1) low Mn Composition Design is adopted, comparatively loose to the requirement of S content, save steel-making cost, reduce steel-making difficulty;
(2) add Sn or/and Sb, improve hydrogen sulfide corrosion-resistant, reduce the addition of Ni, Cu alloy, do not add the precious metals such as Mo, save cost of alloy;
(3) by controlled cooling model speed and final cooling temperature, the steel plate organization type that the present invention produces is polygonal ferrite+corynebacterium grain shellfish tissue, and the more conventional ferrite+pearlitic structure of its hydrogen sulfide corrosion-resistant performance has superiority;
(4) rolling technology window is wider, the plate property produced is stablized, and mechanical property meets the requirement of pipe line steel X65, X70 in API 5L standard: yield tensile ratio≤0.85, elongation after fracture A >=35%,-20 DEG C of ballistic work >=300J ,-20 DEG C of DWTT fiber tearing area >=95%.
(5) hydrogen sulfide corrosion resistance of described steel plate can be: test Properties of HIC resistance by standard NACE TM 0284-2003, CLR, CSR, CTR are 0%; Test anti-SSCC performance by standard NACE TM 0177-2005, sample does not find crackle.
Accompanying drawing explanation
Fig. 1 is the metallurgical structure figure of embodiment light plate;
Fig. 2 is the tissue topography figure of embodiment light plate.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Through X65, X70 pipeline steel continuous casting blank that blast furnace ironmaking → hot metal pretreatment → converter steelmaking → refining → vacuum outgas → continuous casting is produced, through heating → de-scaling → controlled rolling → control cold → air cooling, wherein main technologic parameters is in table 1, make the Wide and Thick Slab that 15.9mm is thick, 5 the numbering experimental steels obtained and the concrete composition of conventional X65 pipe line steel are in table 2, embodiment is finally organized as polygonal ferrite+granular bainite, as shown in Figure 1, under transmission electron microscope, granular bainite microstructure pattern is observed, find that it is corynebacterium, as shown in Figure 2, mechanical property is in table 3.
The main rolling technological parameter of table 1 embodiment of the present invention and comparative example
The chemical composition (wt%) of table 2 embodiment of the present invention and comparative example
C Si Mn P S Nb Ti Cr Ni Cu Al Sn Sb
Embodiment 1 0.05 0.21 0.54 0.006 0.0002 0.042 0.013 0.35 - 0.47 0.035 0.001 0.049
Embodiment 2 0.05 0.19 0.52 0.009 0.0098 0.029 0.019 0.32 0.32 - 0.021 0.048 0.001
Embodiment 3 0.04 0.22 0.39 0.007 0.0007 0.053 0.015 0.38 0.17 0.30 0.035 0.027 0.021
Embodiment 4 0.04 0.17 0.45 0.009 0.0087 0.057 0.014 0.37 0.18 0.26 0.033 0.015 0.037
Embodiment 5 0.03 0.32 0.65 0.005 0.0076 0.046 0.010 0.63 0.10 0.40 0.049 0.032 0.031
Comparative example 0.06 0.22 1.68 0.009 0.0025 0.031 0.014 - - - 0.035 - -
The mechanical property of table 3 embodiment of the present invention and comparative example
Rt0.5，MPa Rm，MPa YR A，％ -20℃Kv，J -20℃DWTT SA，％
Embodiment 1 565 689 0.82 38 346,336,364/348 100,100/100
Embodiment 2 570 704 0.81 41 323,313,325/320 100,100/100
Embodiment 3 525 632 0.83 43 339,348,346/344 100,100/100
Embodiment 4 510 630 0.81 41 319,319,332/323 100,100/100
Embodiment 5 515 657 0.78 42 331,327,335/331 100,100/100
Comparative example 525 615 0.85 48 330,335,324/330 100,100/100
Carry out Properties of HIC resistance test according to NACE TM 0284-2003 standard, testing liquid adopts NACETM 0284A solution, and after 96h test, its Properties of HIC resistance assay is in table 4.
The Properties of HIC resistance assay of table 4 embodiment of the present invention and comparative example
Crack length rate (CLR, %) Crack thickness rate (CTR, %) Crack-sensitivity rate (CSR, %)
Embodiment 1 0 0 0
Embodiment 2 0 0 0
Embodiment 3 0 0 0
Embodiment 4 0 0 0
Embodiment 5 0 0 0
Comparative example 30.7,18.7,26.4/25.3 3.6,2.3,2.5/2.8 2.2,1.4,1.8/1.8
Carry out anti-SSCC performance test according to NACE TM 0177-2005 standard method C, testing liquid adopts NACE TM 0284A solution, and its test-results is in table 5.
The anti-SSCC service check result of table 5 embodiment of the present invention
Stress application (MPa) Yield strength (%) Test-results
Embodiment 1 485 86％ Do not split
Embodiment 2 485 85％ Do not split
Embodiment 3 450 86％ Do not split
Embodiment 4 450 88％ Do not split
Embodiment 5 450 87％ Do not split
From table 3 ~ 5, the resistance to H that the present invention produces 2s corroded pipeline steel plate, has good comprehensive mechanical property, can meet API 5L X65, X70 requirement, and has good hic resistance and anti-SSCC performance, can meet API 5L standard annex H to resistance to H 2the requirement of S corroded pipeline steel.
In addition to the implementation, the present invention can also have other embodiments.The equivalence change that all spirit according to the present invention are done or amendment, all should be encompassed within protection scope of the present invention.
The above embodiment only have expressed the specific embodiment of the present invention, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.Those skilled in the art all drops in protection scope of the present invention any variation that the present invention does under the enlightenment that the present invention conceives.

Claims (4)

1. a resistance to H 2the pipe line steel Wide and Thick Slab of S corrosion, it is characterized in that, chemical composition composition is C:0.018-0.068% by mass percentage, Si:0.12-0.42%, Mn:0.33-0.68%, P :≤0.0098%, S :≤0.0098%, Nb:0.022-0.062%, Ti:0.009-0.021%, Cr:0.28-0.67%, Ni :≤0.32%, Cu :≤0.47%, Alt:0.013-0.057%, also comprise Sn:0.001-0.05%, the one in Sb:0.001-0.05% or two kinds, all the other are iron and inevitable impurity.
2. a resistance to H 2the production method of the pipe line steel Wide and Thick Slab of S corrosion, production technique comprises: blast furnace → hot metal pretreatment → converter → refining → vacuum outgas → continuous casting → heating of plate blank → de-scaling → controlled rolling → control cold → air cooling, it is characterized in that, described hot rolling treats that temperature thickness is 3-5 times of finished product thickness, finishing temperature is 800-850 DEG C, and final cooling temperature is 450-600 DEG C.
3. resistance to H according to claim 2 2the production method of the pipe line steel Wide and Thick Slab of S corrosion, it is characterized in that, in described During Controlled Rolling, hot rolling Heating temperature is 1150-1210 DEG C, and roughing temperature is 980-1080 DEG C, entrance finishing temperature≤960 DEG C, and rate of cooling is 20-30 DEG C/s.
4. the resistance to H according to Claims 2 or 3 2the production method of the pipe line steel Wide and Thick Slab of S corrosion, is characterized in that, the steel metallographic structure at room temperature that described production method is produced is polygonal ferrite and corynebacterium grain shellfish tissue.
CN201510354276.4A 2015-06-25 2015-06-25 Pipeline steel, wide and thick plate, resistant to H2S corrosion, and production method thereof Pending CN104928602A (en)

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CN105821314A (en) * 2016-04-26 2016-08-03 江苏省沙钢钢铁研究院有限公司 Corrosion resistant steel plate for baseplate in cargo oil cabin of crude oil ship and production method thereof
CN107974621A (en) * 2017-12-15 2018-05-01 武汉钢铁有限公司 A kind of economical straight-line joint submerged arc welding tube X80 Pipeline Steel Plates and production method
CN107974622A (en) * 2017-12-15 2018-05-01 武汉钢铁有限公司 Straight-line joint submerged arc welding tube X80 Pipeline Steel Plates and the production method of a kind of thickness >=26.4mm
CN107974614A (en) * 2017-11-23 2018-05-01 武汉钢铁有限公司 The production method of the X80 level pipe line steels of resistance against hydrogen cracking
CN109628842A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 550MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628843A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 450MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628844A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 700MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628841A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 350MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
WO2019233015A1 (en) * 2018-06-04 2019-12-12 南京钢铁股份有限公司 Acid and corrosion-resistant thick-walled large pipeline steel and production method therefor
CN112474801A (en) * 2020-11-09 2021-03-12 江苏省沙钢钢铁研究院有限公司 Wide and thick plate with small trimming loss and production method thereof
CN115074624A (en) * 2022-06-22 2022-09-20 江苏沙钢集团淮钢特钢股份有限公司 Steel for hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube and preparation method thereof
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CN105821314A (en) * 2016-04-26 2016-08-03 江苏省沙钢钢铁研究院有限公司 Corrosion resistant steel plate for baseplate in cargo oil cabin of crude oil ship and production method thereof
CN107974614A (en) * 2017-11-23 2018-05-01 武汉钢铁有限公司 The production method of the X80 level pipe line steels of resistance against hydrogen cracking
CN107974622B (en) * 2017-12-15 2019-07-23 武汉钢铁有限公司 A kind of straight-line joint submerged arc welding tube X80 Pipeline Steel Plate and the production method of thickness >=26.4mm
CN107974621A (en) * 2017-12-15 2018-05-01 武汉钢铁有限公司 A kind of economical straight-line joint submerged arc welding tube X80 Pipeline Steel Plates and production method
CN107974622A (en) * 2017-12-15 2018-05-01 武汉钢铁有限公司 Straight-line joint submerged arc welding tube X80 Pipeline Steel Plates and the production method of a kind of thickness >=26.4mm
CN107974621B (en) * 2017-12-15 2019-07-23 武汉钢铁有限公司 A kind of economical straight-line joint submerged arc welding tube X80 Pipeline Steel Plate and production method
WO2019233015A1 (en) * 2018-06-04 2019-12-12 南京钢铁股份有限公司 Acid and corrosion-resistant thick-walled large pipeline steel and production method therefor
CN109628842A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 550MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628841A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 350MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628844A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 700MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628843A (en) * 2019-02-12 2019-04-16 鞍钢股份有限公司 450MPa grades of transporting coal open-top car corrosion-resisting steels of yield strength and its manufacturing method
CN109628842B (en) * 2019-02-12 2020-05-29 鞍钢股份有限公司 Corrosion-resistant steel with yield strength of 550MPa for coal transportation open wagon and manufacturing method thereof
CN109628841B (en) * 2019-02-12 2020-05-29 鞍钢股份有限公司 Corrosion-resistant steel with yield strength of 350MPa for coal transportation open wagon and manufacturing method thereof
CN109628844B (en) * 2019-02-12 2020-05-29 鞍钢股份有限公司 Corrosion-resistant steel with yield strength of 700MPa for coal transportation open wagon and manufacturing method thereof
CN112474801A (en) * 2020-11-09 2021-03-12 江苏省沙钢钢铁研究院有限公司 Wide and thick plate with small trimming loss and production method thereof
CN112474801B (en) * 2020-11-09 2022-05-17 江苏省沙钢钢铁研究院有限公司 Wide and thick plate with small trimming loss and production method thereof
CN115074624A (en) * 2022-06-22 2022-09-20 江苏沙钢集团淮钢特钢股份有限公司 Steel for hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube and preparation method thereof
CN115572896A (en) * 2022-09-13 2023-01-06 武安市裕华钢铁有限公司 High-toughness and high-corrosion-resistance pipeline steel and production method thereof

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