CN102199736A - High-strength and anti-CO2/H2S corrosion seamless gathering-line pipe - Google Patents

High-strength and anti-CO2/H2S corrosion seamless gathering-line pipe Download PDF

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CN102199736A
CN102199736A CN 201010130911 CN201010130911A CN102199736A CN 102199736 A CN102199736 A CN 102199736A CN 201010130911 CN201010130911 CN 201010130911 CN 201010130911 A CN201010130911 A CN 201010130911A CN 102199736 A CN102199736 A CN 102199736A
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CN102199736B (en
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杨建强
谭谆礼
张忠铧
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Baoshan Iron and Steel Co Ltd
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Abstract

A high-strength and anti-CO2/H2S corrosion seamless gathering-line pipe comprises 0.01-0.1 wt% of C, 0.1-0.5 wt% of Si, 0.1-1 wt% of Mn, P being less than or equal to 0.02 wt%, S being less than or equal to 0.003 wt%, 1.0-7.0 wt% of Cr, 0.1-2 wt% of Mo, 0.1-0.5 wt% of Cu, Ni being larger than or equal to 0.05 wt% and less than or equal to 0.75 wt%, 0.01-0.1 wt% of Cu and A1, Nb being larger than or equal to 0 and less than or equal to 0.1 wt%, V being larger than or equal to 0 and less than or equal to 0.1 wt%, Ti being larger than or equal to 0 and less than or equal to 0.1 wt%, 0.01-0.1 wt% of a rare earth element, and the balance Fe. After a round tube blank is obtained through smelting by using an arc furnace or a converter, a seamless crude pipe is produced by using the Mannesman seamless steel pipe rolling technology; and the crude pipe is modified or treated through a normalising processing technology to produce finished pipes of different steel-grade from X52 to X80. The gathering-line pipe provided by the invention has excellent anti-CO2 corrosion performance, anti-H2S medium sulfide stress cracking (i.e. SSC) and hydrogen-induced cracking (HIC) performance, and excellent welding performance.

Description

A kind of high strength, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool
Technical field
The present invention relates to the collector and delivery pipe spool, particularly a kind ofly be used to carry the high strength of crude corrosively or Sweet natural gas, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool.
Background technology
Because the medium that the collector and delivery pipe spool is carried is crude oil or the Sweet natural gas of handling without desalination, dehydration and desulfurization, thereby generally also requires it to have certain anti-H corresponding strength, impact property and the welding property except that requiring the gathering line pipe to have 2S/CO 2Corrosive nature.In collector and delivery pipe spool field, Japanese iron and steel enterprise has a lot of representational products to be worth us to use for reference.From specific product, anti-CO 2Corrosion collector and delivery pipe spool is more representative with the seamless collector and delivery pipe spool of 1-12Cr series of Sumitomo, and its product has all adopted the composition design system of ultralow C+Mn+Cr+Mo+Nb+V+Ti, and the said products all has certain anti-H2S stress corrosion crack performance simultaneously; At anti-H 2S-CO 2Corrode seamless collector and delivery pipe spool field then with the anti-H of Kawasaki 0-1Cr 2S-CO 2Corrosion collector and delivery pipe spool is more representative, and its composition system is ultralow C+1.5%Mn+0.3-1%Cr+0.02Nb+Ti+V.
Day JP6336639 of the present invention and JP8269623 have set forth the anti-H2S/CO2 corrosion of a kind of low Cr collector and delivery pipe spool, and this line pipe not only has certain anti-CO 2Corrosive nature has also been passed through the anti-HIC service check of NACE-TM0284 defined simultaneously.Yet 0.25～1%Cr content is to the anti-CO of steel grade 2Corrosion and corrosion resistance contribution are very limited, its anti-CO 2Corrosion and corrosion resistance only increase with respect to plain carbon stool, generally domesticly all the steel grade of this composition system are classified as anti-HIC collector and delivery pipe spool.This class steel grade is difficult to satisfy the anti-H of user in harsh day by day oil-gas field Service Environment 2S/CO 2The corrosive double requirements.
The Cr content that day JP55158253 of the present invention, JP55158255, JP55158255 disclose Sumitomo Metal Industries' exploitations from 1% until 12% a series of anti-CO 2Corrosion collector and delivery pipe spool, the anticorrosive collector and delivery pipe spool of this series not only has good anti-CO 2Corrosive nature, also passed through simultaneously 40 ℃, contain 50ppmH 2The CO that S and 180-1000ppm do not wait 2, the four-point bending test in the 5%NaCl solution.Yet anti-HIC check of API-5L standard recommendation NACE-TM0284 and NACE-TM0177 constant load method of inspection test temperature are 24 ± 3 ℃, all stipulate with normal pressure H with above-mentioned two standards simultaneously 2The uninterrupted feeding of S gas makes H in the solution 2S concentration reaches capacity, at this moment H in the solution 2S concentration is generally at 2500～3000ppm; As seen the anti-H of above-mentioned steel grade 2The S check wants loose a lot of than standard code, therefore from stricti jurise, this steel series can not be classified as resisting sulfide stress cracking or anti-HIC steel grade; This series of patents thinks that also the affiliation that adds of Cu reduces anti-CO in addition 2Corrosive nature, this obviously and Cu can promote the film formed common recognition of corrosion product to run counter to protectiveness; Simultaneously, the described steel grade of JP55158255 fails to take into full account the welding property of high Cr steel; At last, the described steel grade of this series of patents has added precious metal elements such as Co, Zr to improve corrosion resistance and welding heat influence area toughness, and this will make that cost improves greatly.
Summary of the invention
The object of the present invention is to provide a kind of high strength, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool, has good anti-CO concurrently 2Corrosive nature, the anti-H that contains 2S medium sulfide stress cracking (SSC) (being SSC) and hydrogen induced cracking (HIC) (HIC) and superior weldability energy.
For achieving the above object, technical scheme of the present invention is,
A kind of high strength, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool, its composition 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%, 0.05≤Ni≤0.75Cu, Al 0.01～0.1%, Nb≤0.1%, V≤0.1%, Ti≤0.1%, rare earth element 0.01%～0.1%, and all the other are Fe;
Wherein: CE Pcm≤ 0.50, CE IIW≤ 1.60,
CE pcm＝C+Si/30+(Mn+Cu+Cr)/20+Ni/60+Mo/15+V/10+5B；
CE? II?W＝C+Mn/6+(Cr+Mo+V)/5+(Ni+Cu)/15。
In the design of the seamless collector and delivery pipe spool of the present invention composition:
Anti-CO 2Corrosive nature: Cr is to improving anti-CO 2Corrosive nature is economy and effective elements the most, and many documents are all described the anti-CO along with the increase steel grade of Cr content 2Corrosive nature is multiplied, and the erosion rate that contains the Cr3% steel grade in same media is not only for containing 1/5 of anti-Cr steel grade; In addition, elements such as Ni, Cu, Mo, Ti all can effectively improve the anti-CO of steel grade 2Corrosive nature.
Anti-H 2S corrosive nature: generally think that all the carbide of alloying element and sulfide can cause the anti-H of steel grade 2The S corrosive descends, this is because the easy attraction hydrogen atom of separating out of carbide and sulfide is assembled around it, thereby the sharp corner that makes around it carbide especially or sulfide easily becomes the formation of crack of hydrogen induced cracking (HIC) and sulfide stress cracking (SSC), cause the steel grade sulfur resistance to descend, so the content of the sulfide of the carbide of alloying elements such as Cr, Mn, V, Ti, Nb and Mn and form often become and influence the anti-H of steel grade 2The key factor of S corrosive nature; Also can reduce the anti-H of steel grade during being added with of Ni 2Therefore the S corrosive nature is generally all added Cu simultaneously and is come balance Ni antagonism H 2The negative impact that the S corrosive nature causes.
Welding property: generally with CE PcmAnd CE II WCharacterize the welding property of steel grade, CE PcmAnd CE IIWLow more then welding property is good more.
CE pcm＝C+Si/30+(Mn+Cu+Cr)/20+Ni/60+Mo/15+V/10+5B
CE? II?W＝C+Mn/6+(Cr+Mo+V)/5+(Ni+Cu)/15
As can be seen, C influences the most significant element of welding property, and in addition elements such as the Si of too high amount, Mn, Cr, Cu, Ni, Mo, V all can cause the decline of welding property.For middle high alloy steel grade, because higher its welding property of alloy content descends unavoidably to some extent, possess good welding property in order to guarantee it, steel grade of the present invention all should guarantee CE Pcm≤ 0.50, CE IIW≤ 1.60.
C is to improving the effective elements of steel grade intensity, but easily forms the carbide of Cr during the C too high levels and separate out at crystal boundary, thereby causes the appearance in the local poor Cr of crystal boundary district to cause the anti-CO of steel grade 2Corrosive nature descends; Simultaneously the easy attraction hydrogen atom of separating out of carbide is assembled around it, thereby makes around it the sharp corner of carbide especially become the formation of crack of hydrogen induced cracking (HIC) and sulfide stress cracking (SSC) easily, causes the steel grade sulfur resistance to descend; Too high C also can cause the steel grade welding property to descend simultaneously.When C content was above greater than 0.1%, this destruction was more remarkable.Therefore, design C content is below 0.1%.
Si is effective reductor, and simultaneously the Si 0.1% or more is useful to the intensity that improves steel grade, still is higher than the reduction that 0.5% Si can cause steel grade toughness and welding property.Therefore, the content of design Si is 0.1～0.5%.
Mn can significantly improve the intensity and the toughness of steel grade, also is effective reductor, and has the effect of taking off S, but too much Mn also can reduce the toughness of steel grade, simultaneously too high Mn can reduce the welding property of steel grade, and in addition, MnS separates out the anti-H that can reduce steel grade greatly 2The S corrosive nature.Therefore, the content of design Mn is 0.1～1%.
P, S are the impurity element of association.P, S produce harmful effect to the hot workability of alloy, purity, and P, S content be respectively 0.02%, 0.003% when above, and the corrosion resistance nature of steel grade is produced tangible destruction.Thereby, the content of design P, S respectively 0.02%, below 0.003%.
Cr, be to improving anti-CO2 corrosive nature economy and effective elements the most, the anti-CO2 corrosive nature that many documents are all described along with the increase steel grade of Cr content is multiplied, the erosion rate that contains the Cr3% steel grade in same media is not only for containing 1/5 of anti-Cr steel grade, when Cr content could be more remarkable in 1% above-mentioned effect when above; But too high Cr content can cause its carbide separating out at crystal boundary, the easy attraction hydrogen atom of separating out of carbide is assembled around it, thereby make around it the sharp corner of carbide especially easily become the formation of crack of hydrogen induced cracking (HIC) and sulfide stress cracking (SSC), cause the steel grade sulfur resistance to descend; Too high Cr content can cause the steel grade welding property to descend simultaneously.
Mo can effectively improve the anti-CO of steel grade 2Corrosion and anti-H 2S corrosive nature and anti-local corrosion performance, thus the interpolation of Mo simultaneously can also improve the welding property that the toughness of welded heat affecting zone is improved steel grade, but the too high levels of Mo can cause cost significantly to improve, therefore, and the content of design Mo is below 2%.
Cu helps the formation of steel grade surface passivated membrane and corrosion products film, thereby improves the anti-CO of steel grade 2Corrosion and anti-H 2The S corrosive nature can also effectively improve the antimicrobial corrosive nature of steel grade simultaneously for subsea pipeline, but the content of Cu surpasses at 0.5% o'clock, and the mechanical property that can reduce steel grade reduces the hot workability of steel grade, anti-H simultaneously 2S corrosive nature and welding property.Thereby the content of design Cu is 0.1%～0.5%.
Ni can effectively promote the anti-CO of steel grade 2Corrosive nature, but the interpolation meeting of Ni is to the anti-H of steel grade 2The S corrosive nature causes negative impact, also can reduce the anti-H of steel grade during being added with of Ni 2Therefore the S corrosive nature is generally all added Cu simultaneously and is come balance Ni antagonism H 2The negative impact that the S corrosive nature causes.Costing an arm and a leg of Ni can significantly increase the cost of alloy of steel grade simultaneously.In order to strengthen the anti-CO of steel grade 2Corrosive improves the anti-H2S corrosive nature of steel grade simultaneously, and steel grade of the present invention generally is controlled at 0.05%≤Ni≤0.75Cu with the content of Ni.
Al is effective reductor, be to be difficult to the alloying element avoided in the steelmaking process, but the content of Al surpasses at 0.1% o'clock, will destroy the toughness and the hot workability of steel grade.Thereby the content of design Al is 0.01%～0.1%.
Nb, V, Ti, have intensive binding ability formation carbide, nitride or carbonitride separately with elements such as C, N, help to improve the mechanical property of steel grade, Ti adds the corrosion resistance that can also strengthen steel grade simultaneously, but when the content of Nb, V, Ti surpasses 0.1%, make that the precipitated phase particle is thick, and make its carbide and nitride inclusion increase, strength at break on the contrary reduces the welding property of steel grade simultaneously.Thereby the content of design Nb, V, Ti is respectively below 0.1%, and more excellent is below 0.07%.
RE：0.01％～0.1％
The interpolation of rare earth element can effectively improve the toughness of steel grade, improves the toughness of welded heat affecting zone simultaneously, but will reduce the welding property of steel grade when ree content surpasses 0.1%, so optimum content should be 0.01%～0.1%.
In order to guarantee that steel grade of the present invention possesses good anti-CO 2The anti-H of burn into 2S corrosion, steel grade of the present invention with Cr content be limited to 1.0%～7.0%, Cu content is limited to 0.1%～0.5%, Ni content is 0.05%≤Ni≤0.75Cu, add 0.1%～2% Mo simultaneously; In order to guarantee that steel grade possesses good welding property, steel grade of the present invention has added the toughness that 0.01%～0.1% rare earth element improves welded heat affecting zone, and steel grade of the present invention in addition all needs to guarantee CE simultaneously Pcm≤ 0.50, CE IIW≤ 1.60.
Obtain circular pipe by continuous casting process after using electric arc furnace or converter+secondary refining process to obtain containing the molten steel of mentioned component, pipe uses rotary heating furnace to be heated to AC 3Or using Mannesman roll seamless steel tube technology to make seamless hollow forging after the above temperature, hollow forging obtains the different grade of steel production tubes of X52～X80 by the thermal treatment process of the normalizing of 850～950 ℃ of quench+580～700 ℃ of tempering or 800～920 ℃.
Beneficial effect of the present invention
The employing mentioned component can be produced the different grade of steel high strength of X52～X80 with manufacture method, anti-CO2/H2S corrodes seamless collector and delivery pipe spool.Compared with prior art, the present invention has following advantage:
1, the anti-H that contains 2S medium SSC and HIC performance.As described in embodiment, compare (Comparative Examples 9 is the described contrast patent of preamble JP56093856 typical composition) with the JP55158253 of Sumitomo Metal Industries, JP55158255, the described steel grade of JP56093856, because steel grade of the present invention is controlled at Cr content 1-7%, Mn content is controlled at 0.1-1%, also adds Cu and Ni simultaneously, thereby guaranteed that steel grade of the present invention can be by anti-HIC check of carrying out in strict accordance with NACE-TM0284 and the constant load check of carrying out according to NACE-TM0177; Because too high Cr, the anti-H that contains of Mn content Comparative Examples 9 described steel grades 2The S corrosive nature then has big gap than steel grade of the present invention; As seen the anti-H of steel grade of the present invention 2The S corrosive nature is greatly improved than the described steel grade of contrast patent.
2, anti-CO 2Corrosive nature.As described in embodiment, compare (Comparative Examples 11 is the described typical composition of JP8269623 among the embodiment) with the described steel grade of Kawasaki Steel JP6336639 and JP8269623, because steel grade of the present invention has higher Cr, Mo content and lower C content, make the erosion rate of steel grade of the present invention in same media only for its 5%～10%, aspect anti-CO2 corrosive nature than increasing exponentially.
3, good welding property.The present invention has adopted the basic ingredient system of Ultra-low carbon+low manganese, and the alloying constituent of strict simultaneously control Cr, Mo, V, Cu, Ni and an amount of alloying elements such as Nb, Ti, rare earth that add make steel grade possess good welding property.As described in embodiment, steel grade of the present invention is guaranteeing anti-CO 2/ H 2The S corrosive nature while, than Comparative Examples 9, steel grade CE of the present invention PcmAnd CE II WThan Comparative Examples 9 reduction is significantly arranged, the heat affected zone mechanical property also is greatly improved simultaneously.As seen its welding property of steel grade of the present invention is greatly improved than the contrast patent.
4, the controllability that possesses high strength and intensity.The present invention possesses the composition system that good welding property has adopted Ultra-low carbon+low manganese content in order to guarantee steel grade, but, guaranteed that steel grade can obtain from the line pipe product of the different grade of steels of X52～X80 by different heat treatment technology simultaneously by rationally adding Cr, Mo, Nb, V, Ti and rare earth element.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Obtain circular pipe by continuous casting process after using electric arc furnace or converter+secondary refining process to obtain containing the molten steel of composition as shown in table 1, pipe uses rotary heating furnace to be heated to AC 3Or using Mannesman roll seamless steel tube technology to make seamless hollow forging after the above temperature, hollow forging obtains the different grade of steel production tubes of X52～X80 by the thermal treatment process of 890～950 ℃ of quench+580～700 ℃ of tempering or 800～920 ℃ of normalizings.
The embodiment of the invention is referring to table 1, and wherein, numbering 1～8 is the embodiment of the invention, and numbering 9～11 is a Comparative Examples.
Comparative Examples 9 is described day JP56093856 typical composition of the present invention of preamble, No. 20 composition of steel that Comparative Examples 10 collector and delivery pipe spools are commonly used, and Comparative Examples 11 is described day JP8269623 typical composition of the present invention of preamble.
Tensile test at room temperature and-10 ℃ of following V breach charpy impact tests are carried out in sampling in these steel pipes, and the mechanical property of the tube material of alloy tubing and casing material of the present invention and reference alloys is listed table 4 in.Use dynamic corrosion weight loss method to the anti-CO of each steel grade of the present invention 2Corrosive nature is tested, anti-CO 2Corrosive nature is to carry out in the corrosive medium of simulation gas field, Fanyu realistic well condition, and test conditions and solution medium composition see Table 2 and table 3 in detail.According to NACE TM0284-2003 the anti-HIC performance of steel grade of the present invention is checked, solution medium is an A liquid; According to NACE TM0177-2003 the anti-SSC performance of steel grade of the present invention is checked, rate of loading is 72%SMYS, and solution medium is an A liquid.Anti-CO 2Corrosive nature and anti-H 2The result is as shown in table 4 for the S corrosive nature.
Figure GSA00000061493800081
The anti-CO of table 2 2The corrosion test condition
Temperature (℃) ?CO 2Partial pressure (MPa) Test period (h) Solution type Speed of rotation (m/s)
60 ?1 ?240 Fanyu simulated solution 1
The component (mg/L) of table 3 Fanyu oil field stratum hydromining fluid
Ion K ++Na + Mg 2+ Ca 2+ Cl - SO 4 2- HCO 3 - CO 3 2- Total mineralization
Concentration 18872 86 142 27632 1334 500 111 48677
The every performance comparison of table 4 embodiment of the invention and Comparative Examples
Figure GSA00000061493800091
From above data as can be seen, the erosion rate of each steel grade of the present invention in Fanyu oil-gas field simulation solution all is lower than 0.45mm/a, and the erosion rate of Comparative Examples 10 described No. 20 steel under the same media condition is about more than 10 times of steel grade of the present invention up to 4.34; Comparative Examples 11 erosion rate under the same conditions is about more than 5 times of steel grade of the present invention up to 2.31mm/a.While steel grade of the present invention has all passed through NACE TM0284-2003 and the described anti-HIC of NACE TM0177-2003 and anti-SSC performance and has checked, and fracture just took place in 340 hours in No. 20 steel in the check of NACE TM0177-2003A method, and fracture just took place at 59 hours Comparative Examples 9 described steel grades.In addition, all greater than 58J, and Comparative Examples 9 only is 27J to each steel grade welded heat affecting zone of the present invention-10 ℃ impact value, and Comparative Examples 10,11 impact values are all less than 50.As seen steel grade of the present invention has more good anti-CO with respect to Comparative Examples 2, H 2S corrosion and welding over-all properties.
The present invention can satisfy the oil field and contain CO 2, H 2The production demand of S crude oil or natural gas transport, intensity can reach the 80ksi grade of steel.The exploitation of steel grade of the present invention is significant in petrochemical complex equal energy source industry, and the present invention has very huge market outlook.

Claims (2)

1. a high strength, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool, its composition 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%, 0.05≤Ni≤0.75Cu, Al0.01～0.1%, 0≤Nb≤0.1%, 0≤V≤0.1%, 0≤Ti≤0.1%, rare earth element 0.01%～0.1%, and all the other are Fe;
Wherein: CE Pcm≤ 0.50, CE IIW≤ 1.60,
CE pcm＝C+Si/30+(Mn+Cu+Cr)/20+Ni/60+Mo/15+V/10+5B；
CE IIW＝C+Mn/6+(Cr+Mo+V)/5+(Ni+Cu)/15。
2. high strength as claimed in claim 1, anti-CO 2/ H 2S corrodes seamless collector and delivery pipe spool, it is characterized in that, and 0≤Nb≤0.07%, 0≤V≤0.07%, 0≤Ti≤0.07%, by weight percentage.
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