CN101054649A - Sulfur erosion resisting steel and smelting method thereof - Google Patents

Sulfur erosion resisting steel and smelting method thereof Download PDF

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Publication number
CN101054649A
CN101054649A CN 200710048765 CN200710048765A CN101054649A CN 101054649 A CN101054649 A CN 101054649A CN 200710048765 CN200710048765 CN 200710048765 CN 200710048765 A CN200710048765 A CN 200710048765A CN 101054649 A CN101054649 A CN 101054649A
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steel
erosion resisting
sulfur
refining
resisting steel
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CN100500917C (en
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陈坤
崔邛
滕建明
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Pangang Group Chengdu Iron & Steel Co Ltd
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Pangang Group Chengdu Iron & Steel Co Ltd
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Abstract

The present invention discloses a sulfur attack resistant steel and its smelting process. Said sulfur attack resistant steel can be used as steal for seamless steel conduit wiring tube, possesses favorable economy and excellent welding performance, can be applied widely for seamless steel conduit wiring tube for oil gas conveying in high acidic oil and gas fields. Said steel has the chemical constituent as follows (based on weight percentage ): C 0.08 -0.14%, Si 0.20 -0.30%, Mn 1.25 -1.45%, Nb 0.03 -0.05, Al 0.02 -0.05,Ti 0.02-0.05, and the rest is Fe and impurities. The present invention possesses the beneficial effects that the matching between the low carbon equivalent weight and the high strength in lateral direction and vertical direction is realized by adding two microalloy elements (Nb and Ti ) and introducing Al, as alloying element, into the sulfur attack resistant steel, and then said sulfur attack resistant steel possesses favorable economy and excellent welding performance, can be applied widely for seamless steel conduit wiring tube for oil gas conveying in high acidic oil and gas fields.

Description

Sulfur erosion resisting steel and smelting process thereof
Technical field
The present invention relates to sulfur erosion resisting steel and smelting process thereof.
Background technology
Anti-H 2S corrosion seamless tube spool is the product of high technology content, and along with the continuous exploitation of oil and gas resource, the sour oil gas field constantly increases, H 2S content is more and more higher, H 2S not only causes the paroxysmal sulfide stress cracking (SSC) of metallic substance, and its toxicity is also threatening life safety, antagonism H 2The grade of steel that S corrosion seamless tube spool requires is also more and more higher, and the corrosion resistance of line pipe is had higher requirement.
For improving the anti-H of line tube steel 2The S corrosive nature, usually the technical measures that adopt are carried out to the branch design and/or improve smelting technology and tube-rolling technique, thermal treatment process etc.
Be 1351187A at publication number, open day be that May 29, the patent No. in 2002 are in 00123128.6 the patent of invention specification sheets, promptly disclose a kind of preparation method of high-cleanness, high-strength and high-toughness steel for gas delivering pipeline.The Chemical Composition of this pipe line steel is that chemical ingredients is: C 0.066～0.086%, Si 0.139～0.339%, Mn 1.23～1.43%, and Ti 0.009～0.029%, and Nb 0.03～0.05%, V 0.03～0.05%, S＜0.0008%, P＜0.0015%, O＜15PPm, N＜30PPm, all the other are iron Fe.Corresponding hot mechanical controlled rolling process system is 1200 ℃ of (heating)-1150 ℃ (open rolling)-(1000 ℃～950 ℃) (rolling)-(900 ℃～830 ℃) (finish to gauge)-(500 ℃～400 ℃) (cold eventually), water-cooled (15～30 ℃/s).Microstructure is the perlite P+M/A constituent element of a spot of quasi-polygonal ferrite+minute quantity of acicular ferrite AF+.The pipe line steel that is obtained by the present invention not only has higher intensity and very high low-temperature impact toughness, and can have good anti-H 2 S stress corrosion ability.
At publication number is 1142309C, Granted publication day is on March 17th, 2004, the patent No. is in 00123185.5 the patent of invention specification sheets, a kind of Ultra-low carbon high tenacity anti-H 2 S X65 level steel for gas delivering pipeline is disclosed, the main chemical compositions of this pipe line steel (weight %) is: C 0.02～0.04%, Si 0.15～0.35%, Mn 1.4～1.6%, Nb 0.03～0.05%, V 0.02～0.04%, Mo 0.2～0.4%, S＜0.0007%, P＜0.0030%, all the other are iron Fe, corresponding hot mechanical controlled rolling process system (TMCP) is 1200 ℃ of (heating)-1150 ℃ (open rolling)-(1000 ℃～950 ℃) (rolling)-(900 ℃～830 ℃) (finish to gauge)-(500 ℃～400 ℃) (cold eventually), water-cooled (15～30 ℃/s).Microstructure is a spot of quasi-polygonal ferrite of acicular ferrite AF++M/A constituent element.The pipe line steel that is obtained by the present invention not only has higher intensity and high low-temperature impact toughness, and has good anti-H 2 S stress corrosion ability;
At present, the anti-H of production 2S corroded pipeline steel mostly is greatly and is used to produce anti-H 2The sheet material of S corrosion welded tube all is used to produce anti-H as above-mentioned two kinds of methods 2S pipe line steel sheet material.And existing anti-H 2S corrosion seamless tube spool, most of steel grades can not be realized low cold crack coefficient (Pcm≤0.23%) composition coupling and the high-intensity problem of solution vertical, horizontal down.Even the minority steel grade is arranged have been realized descending the composition coupling and having solved the high-intensity problem of vertical, horizontal at low cold crack coefficient (Pcm≤0.23%), but, can not produce the sulfur erosion resisting steel pipe line steel economically by what realize with addition of other high price alloying element.The anti-H of X60 level 2S corrodes seamless line-pipes steel and is still blank at present.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of sulfur erosion resisting steel, and this steel can be used as seamless line-pipes steel, has good and economic and good welding property, can be widely used in the oil gas transport seamless spool of peracidity oil-gas field.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: sulfur erosion resisting steel of the present invention, it is characterized in that: the Chemical Composition weight percent of this steel is: C 0.08～0.14%, Si 0.20～0.30%, Mn 1.25～1.45%, Nb 0.03～0.05, Al 0.02～0.05, Ti 0.02～0.05, all the other are Fe and impurity.
P in the described impurity≤0.015, S≤0.005, N≤0.01.
Cold crack FACTOR P cm≤0.22% of this steel, Pcm=C+Si/30+ (Mn+Cr+Cu)/20+Ni/60+Mo/15+V/10+5B.
Carbon equivalent ce V≤0.40% of this steel, CEV=C+Mn/6+ (Cr+Mo+V)/5+ (Ni+Cu)/15.
The smelting process that provides a kind of above-mentioned sulfur erosion resisting steel of another technical problem to be solved by this invention, 1. this method comprises the steps: refining just, molten steel terminal point control C 〉=0.05, P≤0.010, tapping temperature 1620-1660 ℃, tapping process carries out deoxidation alloying, BaSiAlCa add-on 2.5～3.5kg/t, Al piece add-on 1.0～1.5kg/t; 2. refining adopts ladle furnace to carry out external refining, feeds the Al line in the refining process, and Al content in the finished product is controlled in the specialized range, feeds Ca-Si silk 0.5～0.7kg/t, 1595～1610 ℃ of tapping temperatures.
The invention has the beneficial effects as follows, by adding two kinds of micro alloying elements of Nb, Ti, and Al is introduced in the sulfur erosion resisting steel as alloy element, realize that low-carbon-equivalent and vertical, horizontal high strength are complementary, therefore have good and economic and good welding property, can reach the anti-H of X60 level 2S corrodes the requirement of seamless line-pipes steel, therefore can be widely used in the oil gas transport seamless spool of peracidity oil-gas field.Smelting process can accurately be controlled molten steel composition, improves the stability of product, to satisfy the requirement of high quality sulfur erosion resisting steel to steel quality.
Embodiment
Fig. 1 is the metallograph of sulfur erosion resisting steel embodiment 1 of the present invention;
Fig. 2 is the metallograph of sulfur erosion resisting steel embodiment 2 of the present invention;
Fig. 3 is the metallograph of sulfur erosion resisting steel embodiment 3 of the present invention.
Embodiment
The present invention is further described below in conjunction with embodiment.
The Chemical Composition weight percent of sulfur erosion resisting steel of the present invention is: C 0.08～0.14%, Si0.20～0.30%, Mn 1.25～1.45%, Nb 0.03～0.05, Al 0.02～0.05, Ti 0.02～0.05, all the other are Fe and impurity.
P in the described impurity≤0.015, S≤0.005, N≤0.01.
The residual element of this steel: Cu≤0.30%, Ni≤0.25%, Cr≤0.20%, Mo≤0.10%, V≤0.03%, B≤0.0005%, and Cu+Mo+Cr≤0.50%.
Cold crack FACTOR P cm≤0.22% of this steel, Pcm=C+Si/30+ (Mn+Cr+Cu)/20+Ni/60+Mo/15+V/10+5B.
Carbon equivalent ce V≤0.40% of this steel, CEV=C+Mn/6+ (Cr+Mo+V)/5+ (Ni+Cu)/15.
By adding two kinds of micro alloying elements of Nb, Ti, and Al is introduced anti-H as alloy element 2In the S corrosion seamless tube spool steel, realize that low-carbon-equivalent and vertical, horizontal high strength are complementary, therefore have good and economic and good welding property, can be widely used in the oil gas transport seamless spool of peracidity oil-gas field.
1. the smelting process of sulfur erosion resisting steel of the present invention comprises the steps: refining just, molten steel terminal point control C 〉=0.05, P≤0.010, tapping temperature 1620-1660 ℃, carry out deoxidation alloying in the smelting process, BaSiAlCa add-on 2.5～3.5kg/t, Al piece add-on 1.0～1.5kg/t; 2. refining adopts ladle furnace to carry out external refining, feeds the Al line in the refining process, and Al content in the finished product is controlled in the specialized range, feeds Ca-Si silk 0.5～0.7kg/t, 1595～1610 ℃ of tapping temperatures.This smelting process can accurately be controlled molten steel composition, improves the stability of product, to satisfy the requirement of high quality sulfur erosion resisting steel to steel quality.
Embodiment:
1, smelting operation
1.1 just make steel water management
Terminal point control and tapping temperature see the following form:
Grade of steel C P T(℃)
X60 ≥0.05 ≤0.010 1620-1660
Tapping process carries out deoxidation alloying, the BaSiAlCa add-on: by 2.5～3.5kg/t, and Al piece add-on: by 1.0～1.5kg/t
1.2, ladle furnace (LF stove) refining
Feed the Al line, finished product Al is controlled in the specialized range, feed Ca-Si silk 0.5～0.7kg/t.
White slag hold-time 〉=15min, and checked the color of refining slag every 5 minutes.
Tapping temperature: casting φ 220 and following specification, first stove is by 1600～1610 ℃ of controls; Casting φ 280 and above specification, first stove is by 1595～1605 ℃ of controls; Heat can reduce by 5～10 ℃ after second stove reached.
Control Argon intensity keeps the molten steel wriggling, forbids molten steel exposed, blows time 〉=6min only.
2, smelt composition
Smelt composition such as following table:
Heat (batch) number C Si Mn Nb Ti Al P S
0683233 0.08 0.22 1.44 0.03 0.025 0.045 0.012 0.004
0682378 0.11 0.27 1.35 0.036 0.035 0.036 0.008 0.003
0381821 0.14 0.30 1.25 0.048 0.045 0.020 0.012 0.005
3, metallographic structure
Referring to Fig. 1, Fig. 2 and Fig. 3, metallographic structure is tempered sorbite+ferrite, and crystal grain tiny (10.0 grades of grain fineness numbers), and homogeneous microstructure can obtain the performance of high strength and high tenacity, and satisfy anti-H fully 2S corrodes requirement.
4, Performance Detection
Performance test results such as following table:
Heat (batch) number Lot number Surrender (Mpa) Tension (Mpa) Extend (%) -10 ℃ of impact (J) 1 -10 ℃ of impact (J) 2 -10 ℃ of impact (J) 3 -10 ℃ of averages (J)
0683233 H487010101 is vertical 475 570 40 213 221 207 211
H487010101 is horizontal 465 555 41 217 221 210 218
0682378 H456080530 is vertical 480 595 39 236 248 251 245
H456080530 is horizontal 465 565 44 250 237 252 247
0381821 H963060186 is vertical 450 550 40 224 220 206 217
H963060186 is horizontal 445 540 39 228 218 205 217
5, anticorrosive detection
Anticorrosive detected result such as following table:
Detected result
Detect cross dimensions: 20.0mm * 13.0mm Outward appearance is described
Test piece number Section number CLR(％) CTR(％) CSR(％)
1-1 111 0 0 0 The no hydrogen blistering in surface
112 0 0 0
113 0 0 0
On average 0 0 0
1-2 121 0 0 0
122 0 0 0
123 0 0 0
On average 0 0 0
1-3 131 0 0 0
132 0 0 0
133 0 0 0
On average 0 0 0

Claims (8)

1. sulfur erosion resisting steel, it is characterized in that: the Chemical Composition weight percent of this steel is: C 0.08～0.14%, Si 0.20～0.30%, Mn 1.25～1.45%, Nb 0.03～0.05, Al 0.02～0.05, Ti 0.02～0.05, all the other are Fe and impurity.
2. sulfur erosion resisting steel as claimed in claim 1 is characterized in that: P in the described impurity≤0.015, S≤0.005, N≤0.01.
3. sulfur erosion resisting steel according to claim 1 is characterized in that: the residual element of this steel: Cu≤0.30%, Ni≤0.25%, Cr≤0.20%, Mo≤0.10%, V≤0.03%, B≤0.0005%, and Cu+Mo+Cr≤0.50%.
4. sulfur erosion resisting steel according to claim 1 is characterized in that: cold crack FACTOR P cm≤0.22% of this steel, Pcm=C+Si/30+ (Mn+Cr+Cu)/20+Ni/60+Mo/15+V/10+5B.
5. sulfur erosion resisting steel according to claim 1 is characterized in that: carbon equivalent ce V≤0.40% of this steel, CEV=C+Mn/6+ (Cr+Mo+V)/5+ (Ni+Cu)/15.
6. the smelting process of sulfur erosion resisting steel according to claim 1 comprises the steps:
1. refining just, molten steel terminal point control C 〉=0.05, P≤0.010, tapping temperature 1620-1660 ℃, tapping process carries out deoxidation alloying, BaSiAlCa add-on 2.5～3.5kg/t, Al piece add-on 1.0～1.5kg/t;
2. refining adopts ladle furnace to carry out external refining, feeds the Al line in the refining process, and Al content in the finished product is controlled in the specialized range, feeds Ca-Si silk 0.5～0.7kg/t, 1595～1610 ℃ of tapping temperatures.
7. as the smelting process of sulfur erosion resisting steel as described in the claim 6, it is characterized in that: described step is 2. in the refining process, white slag hold-time 〉=15min, and checked the color of refining slag every 5 minutes.
8. as the smelting process of sulfur erosion resisting steel as described in the claim 6, it is characterized in that: 2. in the refining process, control Argon intensity keeps the molten steel wriggling to described step, forbids molten steel exposed, blows time 〉=6min only.
CNB2007100487652A 2007-03-29 2007-03-29 Sulfur erosion resisting steel smelting method Expired - Fee Related CN100500917C (en)

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CN102230128A (en) * 2011-06-02 2011-11-02 首钢总公司 Low-cost X70 pipeline steel plate and preparation method thereof
CN102392181A (en) * 2011-11-11 2012-03-28 江苏华程工业制管股份有限公司 Alloy steel, seamless steel pipe and heat treatment technology of shaped steel pipe
CN102899559A (en) * 2012-10-12 2013-01-30 吉林建龙钢铁有限责任公司 Preparation method of steel for oil delivery pipeline
CN102990030A (en) * 2012-12-17 2013-03-27 南京钢铁股份有限公司 Continuous casting process for controlling semi-macroscopic segregation of H2S corrosion resisting steel casting blank
CN104073731A (en) * 2013-03-27 2014-10-01 鞍钢股份有限公司 Ultrahigh-strength ship plate adopting direct quenching process and producing method thereof
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CN110541109A (en) * 2019-07-26 2019-12-06 邯郸钢铁集团有限责任公司 acid-resistant pipeline steel X60MOS for seabed and production method thereof
CN114921721A (en) * 2022-04-27 2022-08-19 首钢集团有限公司 Pipeline steel plate with excellent hydrogen-induced cracking resistance and preparation method thereof
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CN102230128A (en) * 2011-06-02 2011-11-02 首钢总公司 Low-cost X70 pipeline steel plate and preparation method thereof
CN102392181A (en) * 2011-11-11 2012-03-28 江苏华程工业制管股份有限公司 Alloy steel, seamless steel pipe and heat treatment technology of shaped steel pipe
CN102392181B (en) * 2011-11-11 2013-01-23 江苏华程工业制管股份有限公司 Alloy steel, seamless steel pipe and heat treatment technology of shaped steel pipe
CN102899559A (en) * 2012-10-12 2013-01-30 吉林建龙钢铁有限责任公司 Preparation method of steel for oil delivery pipeline
CN102990030A (en) * 2012-12-17 2013-03-27 南京钢铁股份有限公司 Continuous casting process for controlling semi-macroscopic segregation of H2S corrosion resisting steel casting blank
CN102990030B (en) * 2012-12-17 2014-09-03 南京钢铁股份有限公司 Continuous casting process for controlling semi-macroscopic segregation of H2S corrosion resisting steel casting blank
CN104073731B (en) * 2013-03-27 2017-02-22 鞍钢股份有限公司 Production method for ultrahigh-strength ship plate adopting direct quenching process
CN104073731A (en) * 2013-03-27 2014-10-01 鞍钢股份有限公司 Ultrahigh-strength ship plate adopting direct quenching process and producing method thereof
CN104946975A (en) * 2015-07-13 2015-09-30 攀钢集团成都钢钒有限公司 Raw material steel of seamless steel pipe for drill pipe of rotary drilling rig and smelting method of raw material steel
CN106011651A (en) * 2016-08-05 2016-10-12 攀钢集团成都钢钒有限公司 Super strength seamless steel tube for rotary drilling rig drill pipe and production method thereof
CN107747035A (en) * 2017-10-24 2018-03-02 上海大学 Hydraulic oil tube steel, high-pressure oil pipe and preparation method thereof
CN107747035B (en) * 2017-10-24 2020-06-26 上海大学 Steel for high-pressure oil pipe, high-pressure oil pipe and preparation method thereof
CN110541109A (en) * 2019-07-26 2019-12-06 邯郸钢铁集团有限责任公司 acid-resistant pipeline steel X60MOS for seabed and production method thereof
CN110541109B (en) * 2019-07-26 2021-10-15 邯郸钢铁集团有限责任公司 Acid-resistant pipeline steel X60MOS for seabed and production method thereof
CN114921721A (en) * 2022-04-27 2022-08-19 首钢集团有限公司 Pipeline steel plate with excellent hydrogen-induced cracking resistance and preparation method thereof
CN114921721B (en) * 2022-04-27 2023-08-08 首钢集团有限公司 Pipeline steel plate with excellent hydrogen induced cracking resistance and preparation method thereof
CN115807193A (en) * 2022-12-23 2023-03-17 安徽马钢重型机械制造有限公司 'Suhua' continuous casting roller blank material system and preparation method thereof
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