CN101775556A - X65 hot-rolled coil for use in acidic environment and manufacturing method thereof - Google Patents
X65 hot-rolled coil for use in acidic environment and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to an X65 hot-rolled coil for use in an acidic environment and a manufacturing method thereof. The X65 hot-rolled coil comprises the following components by weight percent: 0.02-0.06 weight percent of carbon, 0.15-0.25 weight percent of silicon, 0.80-1.20 weight percent of manganese, 0.02-0.05 weight percent of niobium, 0.020-0.040 weight percent of vanadium, 0.010-0.020 weight percent of titanium, less than or equal to 0.30 weight percent of copper, less than or equal to 0.30 weight percent of nickel, 0.10-0.30 weight percent of Cr, less than or equal to 0.015 weight percent of phosphorus, less than or equal to 0.0015 weight percent of sulfur, 0.0020-0.0050 weight percent of calcium, more than or equal to 2.0 weight percent of Ca/S, less than or equal to 0.0005 weight percent of boron and less than or equal to 0.006 weight percent of nitrogen. Other components are ferrum and trace impurities. The steelmaking process route and key control points are hot metal pretreatment, converter steelmaking, LF furnace refining, RH furnace refining, slab casting, billet finishing and storage. The refining procedures outside the furnaces comprise Ca treatment to modify inclusions. The key points of the rolling process are as follows: the heating temperature is 1150-1200 DEG C, the rough rolling outlet temperature is 920-1020 DEG C, the final rolling temperature is 780-860 DEG C, and the rolling temperature is 560-620 DEG C. The invention adopts low-price alloy (Cr and V) to substitute expensive alloy (Mo and Nb) so as to produce steel hot-rolled coils for X65 pipelines with more stable performance and lower alloy cost. Moreover, the hot-rolled coils for X65 pipelines have anti-HIC performance, high strength and high toughness.
Description
Affiliated field
The present invention relates to a kind of X 65 hot-rolled coil for use in acidic environment and manufacture method thereof, belong to iron and steel novel material and steel rolling field, be specially adapted to high pressure under the sour environment, long-distance transmission pipeline pipe line steel.
Background technology
At present transfer oil, Sweet natural gas with steel pipe all with reference to API API 5L standard, comprise effective hot-rolled coil of spiral submerged arc welded and straight-line joint submerged arc welding tube steel plate, follow hot continuous rolling unit width to increase, also adopt the hot-rolled coil opening plate to produce straight-line joint submerged arc welding tube.Follow transfer pressure increase, conveying to contain H
2The oil of S, gas medium have proposed higher performance requriements to long apart from conveying steel pipe and pipe line steel, require pipe line steel to have higher intensity and good low-temperature impact toughness on the one hand, and promptly high-pressure delivery pipeline steel has good crack arrest characteristic; On the other hand, contain H for conveying
2The oil of S, gas medium require pipe line steel to possess anti-HIC (Hydrogen Induce Crack hydrogen induced cracking) performance.
According to the mechanism that HIC produces, under operating pressure, hydrogen is trapped in lattice at the interface after entering the steel surface, and the prolate strip MnS that forms when particularly rolling is mingled with at the interface, and hydrogen atom forms hydrogen molecule, produces internal stress at this place.Because hydrogen pressure constantly increases, cause the lattice viscous deformation, cause hydrogen further to assemble, the pressure that produces when the hydrogen concentration of habitat has surpassed the elastic deformability at habitat interface, produces tension set, has formed along being mingled with the hydrogen induced cracking that direction distributes.
Contain H in high-pressure delivery
2In the Sweet natural gas of S, avoid hydrogen induced cracking to produce, must reduce or avoid the hydrogen atom gathering place, just control the generation of nonmetallic inclusionsin steel and banded structure, the especially generation of MnS inclusion; Adopt Ca to handle in addition, carry out the inclusion distortion, particularly forming indeformable nodularization inclusion also is one of improvement measure.Therefore, develop anti-HIC type pipe line steel major measure:
1) inclusion in the control steel.Reduce inclusion on the one hand as far as possible, especially control the MnS inclusion in the steel; On the one hand by adopting Ca to handle the nodule that the strip sulfide of minute quantity is converted into unchangeability.
2) reduce strand segregation and product banded structure.Adopt casting blank solidification end dynamically gently to depress technology and can effectively reduce the continuously cast bloom segregation; Reduce carbon content and manganese content and can significantly reduce even eliminate banded pearlitic structure, this tissue also is to cause pipe line steel to produce one of key reason of hydrogen induced cracking.
3) organizational controls.The X65 room temperature texture of general anti-HIC is few pearlitic structure, and promptly tissue all is tiny, uniform polygonal ferrite tissue substantially, perhaps is acicular ferrite structure.
Domestic disclosed patent CN 1811002 " X 65 pipeline steel for use in acid condition and manufacture method thereof " adopts Ca to handle and little Ti treatment process, and strict control P, S content are produced anti-HIC X65 pipe line steel in batches.The subject matter that exists: 1) the expensive alloys addition is 0.05～0.07% than higher as Nb microalloy addition, and the Mo addition is 0.05～0.20%; 2) Mn alloy addition level height reaches 1.50%, is prone to the MnS segregation, and antiacid corrosive power reduces.
Summary of the invention
The purpose of this invention is to provide a kind of X 65 hot-rolled coil for use in acidic environment and manufacture method thereof, the problem that solves is: at present iron and steel situation, adopt cheap alloy (Cr, V) to substitute expensive alloys (Mo, Nb) the anti-HIC performance that production performance is more stable, cost of alloy is lower, high strength and high tenacity X65 pipeline steel hot-rolled coil.
Technical solution of the present invention is:
1, a kind of X 65 hot-rolled coil for use in acidic environment, composition design weight per-cent is: carbon: 0.02～0.06wt%; Silicon: 0.10～0.30%; Manganese: 0.80wt%～1.20wt%; Niobium: 0.02～0.05wt%; Vanadium: 0.020～0.040wt%; Titanium: 0.010～0.020wt%; Copper :≤0.30wt%; Nickel :≤0.30wt%; Cr:0.10～0.30wt%; Phosphorus :≤0.015wt%; Sulphur :≤0.0015wt%; Calcium: 0.002～0.0050; Ca/S 〉=2.0; Boron :≤0.0005wt%; Nitrogen :≤0.006%;
Other is iron and trace impurity.
The effect and the strengthening mechanism of composition design main adding elements of the present invention are as follows:
Carbon: most economical, the most basic strengthening element in the steel, significantly improve intensity, the especially tensile strength of steel by solution strengthening and precipitation strength, but the increase of C content significantly reduces ductility, toughness and the welding property of steel; And C promotes the formation of banded pearlitic structure, significantly reduces anti-HIC performance.Therefore, anti-HIC series pipe line steel C content is generally less than 0.06%, and C content of the present invention is 0.02～0.06%, and target is 0.04%.
Manganese: by the intensity of solution strengthening raising steel, especially tensile strength is that compensation reduces the loss of strength that causes in the pipe line steel because of C content; Secondly Mn enlarges phase region, reduces γ → α transformation temperature, helps to obtain tiny phase-change product, improves obdurability.But Mn has following shortcoming: 1) promote pearlitic structure to form, form banded pearlitic structure easily; 2) Mn increases the center segregation that is easy to occur steel plate.Therefore, for anti-HIC series pipe line steel, reduce Mn and will significantly improve anti-HIC performance, difficult point is how to remedy Mn to reduce the loss of strength that causes, especially tensile strength.The addition of Mn must be taken all factors into consideration the addition of C, the balance of carbon and manganese addition as shown in Figure 1, and promptly carbon content is that 0.06% o'clock Mn content is preferably lower than 1.25%.
Niobium: the most basic microalloy element in the high intensity levels pipe line steel, the refined crystalline strengthening effect is remarkable, can improve obdurability simultaneously.Utilize the towing effect of solid solution Nb and Nb (C, N) precipitate hinders answer, recrystallize and the grain growth of deformed austenite, particularly the finish rolling stage non-recrystallization district the low temperature gross distortion can significantly reduce grain-size after the phase transformation.But undissolved Nb can not bring into play strengthening effect before rolling, reduces the meltage that C and N content can significantly promote Nb, reduces C, N and Nb simultaneously, and the Nb solvent temperature is reduced to the Heating temperature reduction and creates conditions, further energy efficient.But because at present Nb microalloy price is brought up to present 220,000 yuan/ton by 100,000 yuan/ton in 2009, production cost pressure strengthens, so Nb addition of the present invention is 0.02～0.05%, and target is 0.04%.
Titanium: at first Ti can consolidate N, improves low-temperature impact toughness; Next is that the TiN that forms in the sheet billet continuous casting process can effectively hinder in the reheat process austenite crystal and grows up, and improves obdurability; TiN improves the impelling strength of welded heat affecting zone in addition.Ti addition of the present invention is 0.010～0.020%.
Molybdenum: enlarge the γ phase region, proeutectoid ferrite forms when significantly postponing γ → α phase transformation, promotes acicular ferrite structure and avoids the generation of banded structure.But because molybdenum alloy costs an arm and a leg, be up to 400,000/ton, the molybdenum ton steel cost of interpolation 0.2% increases nearly 1000 yuan.
Sulphur, phosphorus: be unavoidable impurities element in the steel, wish low as much as possible.By external refining and Ca processing controls technology, S may be controlled to less than 15ppm on the one hand at present, can become sulfide inclusion on-deformable spherical on the one hand.The main harm of phosphorus is that segregation is serious.The content of S of the present invention is controlled to be≤and 0.0015%; The content of P is controlled to be≤and 0.015%.
Copper, nickel: main strengthening mechanism is solution strengthening, and Cu can improve the solidity to corrosion of steel simultaneously, and the adding of Ni mainly is to improve the red brittleness that Cu causes in steel, and can improve low-temperature impact toughness.Cu target addition of the present invention is 0.15%, and Ni target addition is 0.10%.
Vanadium: have stronger precipitation strength effect and more weak refined crystalline strengthening effect, the coiling temperature promotion is tiny by controlling, (C N) changes thing and separates out the V of disperse, can improve yield strength and tensile strength, particularly tensile strength simultaneously, improves the yield tensile ratio performance.V addition of the present invention is 0.03%.
Chromium: at first Cr has significant solid solution strengthening effect, can remedy because C, Mn reduce the strength degradation that causes, especially tensile strength reduces; Secondly Cr reduces γ → α transformation temperature, can obtain tiny phase-change product, improves obdurability.Cr addition of the present invention is 0.15%.
The innovation point:
The composition design philosophy of 1) adopt low-carbon (LC), hanging down manganese.Carbon content is: 0.02～0.06%, and manganese content: 0.8～1.2%, target Mn content is 1.0%.Reduce Mn content and will lose intensity, but reduce the center segregation of steel, improve anti-HIC performance.
2) add microalloy V (0.03%) and substitute the expensive microalloy Nb of part (0.04%), V iron alloy price is 110,000/ton at present, Nb iron price is 220,000/ton, and the main strengthening effect of V microalloy is a precipitation strength, the main strengthening effect of Nb microalloy is a refined crystalline strengthening, adds a certain amount of V and can remedy owing to C, and Mn content reduces the loss of strength that causes, improve tensile strength, reduce the yield tensile ratio performance.
3) the Cr alloy of interpolation 0.15%.At first the Cr alloy has and Mn alloy phase solid solution strengthening effect together, but does not have the segregation problem; Secondly Cr increases hardening capacity, and part substitutes the strengthening effect of expensive alloys Mo control phase transformation, reduces production costs.
2, the operational path of the manufacture method of a kind of X 65 hot-rolled coil for use in acidic environment of the present invention: hot metal pretreatment → converter steelmaking → LF stove refining → RH stove refining → slab cast → steel billet finishing → process furnace heating → controlled rolling → controlled chilling → batch → check, put in storage, control steel rolling process parameter is as follows: Heating temperature: 1150～1200 ℃; Roughing final temperature: 920～1020 ℃; Finish rolling final temperature: 780～860 ℃; 6 frame low temperature controlled rollings are adopted in finish rolling, and total deformation is greater than 75%; Coiling temperature: 560～620 ℃.
Concrete key point:
1) hot metal pretreatment guarantees S content less than 0.005%, target 0.003%;
2) converter smelting LF enters the station S content less than 0.0040%, and control S content is 8-12ppm behind the RH, and the Ca/S ratio is greater than 2.0;
3) adopt that casting blank solidification end is dynamically gently depressed, control techniquess such as stable superheating temperature, constant pulling rate and liquid level fluctuation of crystallizer ± 3mm, reduce or avoid segregation;
4) Heating temperature is set at 1150～1200 ℃, obtains according to Nb, V solubility product formula;
5) roughing final temperature: 920～1020 ℃, the finish rolling final temperature: 780～860 ℃, finishing stand adopts 6 frames rolling, and passage total reduction (total deformation) is greater than 0.75%;
6) coiling temperature: 560～620 ℃, promote separating out of Nb, V carbonitride.It is about 600 ℃ that carbonitride the best of V microalloy is separated out temperature, and target temperature is controlled to be 590 ± 30 ℃, has both utilized to batch the back coil of strip and be similar to heat insulation effect and promote separating out of V, controls coiling temperature again and is lower than 600 ℃ and guarantees that precipitates are tiny.
Practical application effect of the present invention: " a kind of manufacture method of X 65 hot-rolled coil for use in acidic environment " produces the X 65 hot-rolled coil for use in acidic environment of 18000 tons of anti-HIC according to the present invention, and over-all properties satisfies following technical requirements:
1) tensile property Rt 0.5:460～600MPa, Rm:535～730, Rt0.5/Rm ratio≤0.92, A% 〉=25
2) v-notch impact property
Test temperature :-10 ℃, 10 * 10 * 55mm, the ballistic work mean value 〉=120J of v-notch sample, shear area 100%;
3) DWTT performance.-15 ℃, shear area SA 〉=85%;
4) hardness test: HV10≤230;
5) metallographic structure: grain fineness number is 10 grades or thinner;
6) anti-HIC performance.
Respectively get one of longitudinal test piece in steel plate width 1/4 and 1/2 position and edges of boards, test is according to NACE TM0284-96 standard, A solution (the 5%NaCl+0.5%CH3COOH solution that contains saturated H2S is provided, PH=3) and B solution (the artificial seawater solution that contains saturated H2S, PH=5) test conditions soaked 96 hours down.Condition: check and accept: the responsive rate (CSR)≤2% of crackle, crack length rate (CLR)≤15%, crack thickness rate (CTR)≤5%.
Economic implications of the present invention and social effect:
The anti-HIC X65 hot-rolled coil ton Steel Alloy cost that adopts the present invention to produce reduces 300-500 unit, remarkable in economical benefits.Because present minable larger hydrocarbon field field conditions more and more worsens, and is in the deep layer geologic condition especially, generally contains H2S, it is remarkable with the development need social effect that the steel hot-rolled coil meets China's oil-gas mining to develop anti-HIC high-strength line-pipe.
Description of drawings:
Fig. 1 is the state diagram of a kind of X 65 hot-rolled coil for use in acidic environment and manufacture method carbon thereof, manganese addition;
Fig. 2 is a kind of metallographic structure figure of X 65 hot-rolled coil for use in acidic environment.
Embodiment
Operational path: hot metal pretreatment → converter steelmaking → LF stove refining → RH stove refining → slab cast → steel billet finishing → warehouse-in, check → process furnace heating → controlled rolling → controlled chilling → batch → check, put in storage.
Actual smelting chemical composition is as shown in table 1, and concrete steel rolling process parameter is as shown in table 2, and table 3 is the mechanical properties test result, and table 4 is A solution and B solution assay.
The anti-HIC X65 of table 1. chemical ingredients, wt%
Table 2. steel rolling process parameter
| Sequence number | Heating temperature ℃ | Roughing temperature out ℃ | Finishing temperature ℃ | Rate of cooling ℃/s | Coiling temperature ℃ |
| ??1 | ??1182 | ??938 | ??820 | ??16 | ??576 |
| ??2 | ??1180 | ??942 | ??816 | ??17 | ??568 |
| ??3 | ??1160 | ??956 | ??812 | ??16 | ??602 |
| ??4 | ??1174 | ??948 | ??808 | ??20 | ??583 |
| ??5 | ??1176 | ??952 | ??832 | ??18 | ??565 |
| ??6 | ??1196 | ??940 | ??836 | ??16 | ??562 |
| ??7 | ??1192 | ??947 | ??827 | ??19 | ??570 |
| ??8 | ??1186 | ??962 | ??832 | ??17 | ??593 |
| ??9 | ??1185 | ??943 | ??830 | ??18 | ??590 |
Table 3. mechanical properties test result
Table 4.HIC assay
The anti-HIC X65 hot-rolled coil metallographic structure of adopting the present invention to produce is the pearlitic structure of polygonal ferrite tissue+minute quantity, grain fineness number is 13 grades, be the electromicroscopic photograph of anti-HICX65 hot-rolled coil as shown in Figure 2, pearlitic structure for tiny, uniform polygonal ferrite tissue and minute quantity does not have banded structure.
Can find that from assay anti-HIC X65 hot-rolled coil P, S content that the present invention produces are controlled to be respectively below 0.010% and 0.0010%.The product tensile property is stable, and particularly-10 ℃ Charpy-V impact power is almost all greater than 400J, and hardness performance HV10 is lower than 190.A solution and B Solution H IC assay CLR%, CTR% and CSR% all are zero, flawless.
Adopt the X65 pipe line steel of the anti-HIC of the present invention's production to have the low advantage of cost of alloy, particularly adopt cheap Cr and V alloy to substitute the Mo and the Nb alloy of costliness, meet the strategy of sustainable development.
Claims (2)
1. X 65 hot-rolled coil for use in acidic environment, composition design weight per-cent is: carbon: 0.02～0.06wt%; Silicon: 0.10～0.30%; Manganese: 0.80wt%～1.20wt%; Niobium: 0.02～0.05wt%; Vanadium: 0.020～0.040wt%; Titanium: 0.010～0.020wt%; Copper :≤0.30wt%; Nickel :≤0.30wt%; Cr:0.10～0.30wt%; Phosphorus :≤0.015wt%; Sulphur :≤0.0015wt%; Calcium: 0.002～0.0050; Ca/S 〉=2.0; Boron :≤0.0005wt%; Nitrogen :≤0.006%; Other is iron and trace impurity.
2. the manufacture method of a kind of X 65 hot-rolled coil for use in acidic environment as claimed in claim 1, it is characterized in that: operational path is hot metal pretreatment → converter steelmaking → LF stove refining → RH stove refining → slab cast → steel billet finishing → process furnace heating → controlled rolling → controlled chilling → batch → check, put in storage, and control steel rolling process parameter is as follows: Heating temperature: 1150～1200 ℃; Roughing final temperature: 920～1020 ℃; Finish rolling final temperature: 780～860 ℃; 6 frame low temperature controlled rollings are adopted in finish rolling, and total deformation is greater than 75%; Coiling temperature: 560～620 ℃.
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| CN102212751A (en) * | 2011-06-03 | 2011-10-12 | 首钢总公司 | Steel for high-strength petroleum casing pipe used in heavy oil thermal recovery well and manufacturing method thereof |
| CN102747292A (en) * | 2012-07-31 | 2012-10-24 | 首钢总公司 | Normalized acid-resistant pipeline steel X52NS hot rolled plate coil and producing method thereof |
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| CN103993241A (en) * | 2014-05-30 | 2014-08-20 | 秦皇岛首秦金属材料有限公司 | Hot-rolled flat plate for composite acid-resistant pipeline steel base and production method thereof |
| CN106498279A (en) * | 2016-10-14 | 2017-03-15 | 武汉钢铁股份有限公司 | A kind of economical X65 pipe line steels of low Cr of anti-CO2 corrosion and production method |
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| CN102747292A (en) * | 2012-07-31 | 2012-10-24 | 首钢总公司 | Normalized acid-resistant pipeline steel X52NS hot rolled plate coil and producing method thereof |
| CN102747292B (en) * | 2012-07-31 | 2015-04-22 | 首钢总公司 | Normalized acid-resistant pipeline steel X52NS hot rolled plate coil and producing method thereof |
| CN103667875A (en) * | 2013-08-15 | 2014-03-26 | 首钢京唐钢铁联合有限责任公司 | Preparation method of low-carbon acid-resistant pipeline steel |
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