CN104532132A - High-strength low-alloy oil well pipe for resisting stress corrosion of hydrogen sulfide and manufacture method of high-strength low-alloy oil well pipe - Google Patents
High-strength low-alloy oil well pipe for resisting stress corrosion of hydrogen sulfide and manufacture method of high-strength low-alloy oil well pipe Download PDFInfo
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Abstract
The invention discloses a high-strength low-alloy oil well pipe for resisting stress corrosion of hydrogen sulfide. The oil well pipe comprises the following chemical elements by weight percent: 0.16 to 0.40 percent of C, 0.1 to 0.5 percent of Si, 0.2 to 0.6 percent of Mn, 0.01 to 0.1 percent of Al, 0.01 to 0.05 percent of Nb, more than 0.2 percent of Cr, more than 0.2 percent of Mo, 0.03 to 0.2 percent of V, and the balance of Fe and unavoidable impurities, wherein the weight percentage of each chemical element also satisfies the following condition: (0.35Cr+0.85Mo+2.8V) is more than or equal to 1, (2.4Cr+1.1Mo+4.5V) is less than or equal to 3. The invention also provides a manufacture method of the high-strength low-alloy oil well pipe for resisting the stress corrosion of hydrogen sulfide. The oil well pipe is relatively high in strength and good in H2S stress corrosion resistance, the yield strength of the oil well pipe is more than or equal to 110Ksi, and the K<lSCC> value is more than or equal to 30Mpa*m<1/2>.
Description
Technical field
The present invention relates to a kind of tube product and manufacture method thereof, particularly relate to a kind of oil well pipe and manufacture method thereof.
Background technology
Containing H
2in the oil-gas mining environment of S, use is usually needed to possess certain anti-H
2the material of S stress corrosion performance.Along with continuing to increase of the oil and gas exploitation degree of depth, the requirement of strength for tubing used improves constantly, but the strength of materials is higher, and its stress corrosion opening cracking maleate sensitivity also promotes thereupon.Current deep-well, ultra deep well oil well pipe intensity, usually at more than 110Ksi, require that the material with such high strength will reach higher anti-H
2s stress corrosion performance is very difficult.
Publication number is CN101724785A, publication date is on June 9th, 2010, name is called that the Chinese patent literature of " a kind of ultrahigh-strength hydrogen sulfide corrosion resistant oil well pipe and production method thereof " relates to a kind of oil well pipe tubing, its each chemical element composition (wt.%) is: C:0.25 ~ 0.40%, Si:0.1 ~ 0.5%, Mn:0.3 ~ 1.0%, Cr:0.1 ~ 0.8%, Mo:0.5 ~ 1.2%, V:0.05 ~ 0.15%, Nb:0.3 ~ 0.6%, Ti:0.01 ~ 0.1%, P≤0.015%, S≤0.010%, Al:0.01 ~ 0.05%, all the other are Fe and inevitable impurity.But, the Nb containing high level in the oil well pipe described in this Chinese patent literature.
Publication No. is JPH06-116635A, date of publication is on April 26th, 1994, name is called that the Japanese documentation of " a kind of production has High-Strength Low-Alloy and the manufacture method of the oil well pipe of excellent halophile stress corrosion cracking " discloses a kind of pipe fitting, its chemical element mass percentage is the composition composition of (wt.%): C:0.20 ~ 0.30%, Si:0.10 ~ 1.00%, Mn:0.40 ~ 1.50%, P :≤0.015%, S :≤0.005%, Ni:0.30 ~ 1.20%, Cr:0.50 ~ 1.50%, Mo:0.10 ~ 2.00%, Al:0.001 ~ 0.10%, B:0.0005 ~ 0.0050%, N :≤0.005%, add Ti:0.10 ~ 2.00%, Nb:0.01 ~ 0.10%, one of them in V:0.01 ~ 0.10% is planted.Oil well steel disclosed in this Japanese documentation with the addition of Ni element.
Publication number is US2007/0012383A1, and publication date is on January 18th, 2007, and the american documentation literature that name is called " a kind of manufacture has the method for erosion resistance low alloy steel " discloses a kind of good corrosion resistance and the manufacture method of the low steel grade of alloy content.The mass percentage of each chemical element of this steel grade is: C:0.1 ~ 0.55%, Si:0.05 ~ 0.5%, Mn:0.1 ~ 1%, S:0.0001 ~ 0.005%, Al:0.005 ~ 0.08%, Ti:0.005 ~ 0.05%, Cr:0.1 ~ 1.5%, Mo:0.1 ~ 1%, O:0.0004 ~ 0.005%, Ca:0.0005 ~ 0.0045%, Nb:0 ~ 0.1%, V:0 ~ 0.5%, B:0 ~ 0.005%, Zr:0 ~ 0.10%, P≤0.03%, and N≤0.006%, surplus is made up of Fe and impurity.In the tool steel described in this american documentation literature, both with the addition of N element, with the addition of again Ca element.
The alloy total content of the steel pipe disclosed in above-mentioned three sections of patent documentations is all more than 3wt.%.In addition, these three kinds of steel pipes all do not produce by simple quenching-tempering heat treatment process the pipe fitting meeting mechanical property requirements.
Summary of the invention
The object of the present invention is to provide a kind of High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe, it possesses higher intensity and good anti-H
2s stress corrosion performance (i.e. sulfur resistance).Yield strength>=the 110Ksi of this oil well pipe, simultaneously its K
1SCCvalue>=30Mpa*m
1/2(K
1SCCbe stress corrosion door hurdle value, refer to that the minimum stress-intensity factor destroyed occurs for material or part when stress corrosion.Its unit is MPam
1/2)
To achieve these goals, the invention provides a kind of High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe, its chemical element percent mass proportioning is:
C：0.16～0.40％；
Si：0.1～0.5％；
Mn：0.2％～0.6％；
Al：0.01～0.1％；
Nb：0.01～0.05％；
Cr：>0.2％；
Mo：>0.2％；
V：0.03～0.2％；
Mass percentage also demand fulfillment 0.35Cr+0.85Mo+2.8V >=1 of each chemical element simultaneously,
2.4Cr+1.1Mo+4.5V≤3；
Surplus is Fe and other inevitable impurity.
In the technical program, inevitable impurity mainly refers to P element, S element, O element and N element, wherein, and can control P≤0.02wt.%, control S≤0.003wt.%, control O≤0.01wt.% and control N≤0.008wt.%.
The principle of design of each chemical element in High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention is:
C:C is the important element of proof strength and hardening capacity.When C content is less than 0.16wt.%, intensity is difficult to ensure on the one hand, is difficult to the precipitation avoiding proeutectoid ferrite on the other hand, thus can affects the sulfur resistance of steel.When C content is greater than 0.40wt.%, during quenching, easily there is crackle, also can increase the precipitation tendency of the thick carbide of crystal boundary simultaneously.Therefore, in High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention, need to control C content to control between 0.16 ~ 0.40wt.% scope.
Si: when Si content is more than 0.5wt.%, significantly can increase the cold short tendency of steel, and when its content is lower than 0.1wt.%, then be difficult to ensure deoxidation effect.For oil well pipe of the present invention, need Si content to be limited between 0.1 ~ 0.5wt.% scope.
Mn:Mn has expansion austenite phase field, increases hardening capacity, the beneficial effects such as crystal grain thinning.But Mn easily segregation occurs when solidifying, thus can make to produce obvious banded structure in end product, again because the hardness between banded structure and matrix, precipitated phase all also exist obvious difference, this can affect the sulfur resistance of steel.Given this, need the addition of Mn to be set as 0.2 ~ 0.6wt.%.
Al:Al is the necessary element of steel-deoxidizing.But once Al content more than 0.1wt.%, can have a negative impact to casting cycle.At this, Al content should be set as 0.01 ~ 0.1wt.%.
Nb:Nb is effective crystal grain thinning element.The refinement of crystal grain all has positive effect for the obdurability and sulfur resistance improving steel.Thus, for technical scheme of the present invention, the addition of Nb element needs control to be 0.01 ~ 0.05wt.%.
Cr/Mo/V:Cr, Mo and V are the forming element of strong carbide, and the disperse educt strengthening of its carbide in drawing process is the requisite item that steel obtain higher intensity.That is, obtain enough hardening capacity and strengthening effect, need to add three kinds of elements, usual Cr and Mo needs respectively to add more than 0.2wt.% just obvious strengthening effect, and V needs the amount added could produce strengthening effect when more than 0.03wt.% simultaneously.But, if when V add-on is too much, then thick carbide be can form, thus toughness and the sulfur resistance of material reduced.In addition, the precipitating reinforcing effect of V reaches capacity when its addition is 0.2wt.% state.Based on this, being set as the content of Cr/Mo/V element in technical scheme of the present invention: Cr>0.2wt.%, Mo>0.2wt.%, V:0.03 ~ 0.2wt.%.
Based on the principle of design of above-mentioned each chemical element, the mass percentage of related chemistry element also demand fulfillment relational expression (1) and relational expression (2) in High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention.Wherein, in order to still possess the high strength of 110Ksi after ensureing the high tempering of material more than 670 DEG C, demand fulfillment relational expression (1), i.e. 0.35Cr+0.85Mo+2.8V>=1; Again in order to ensure that the intensity of material is while reaching 110Ksi, excellent anti-H can also be possessed
2s stress corrosion performance (K
1SCCvalue>=30MPa*m
1/2), then demand fulfillment relational expression (2), i.e. 2.4Cr+1.1Mo+4.5V≤3.
What technical scheme of the present invention was taked is add the alloying elements such as Cr, Mo and V in right amount, retrain the mode of its conspiracy relation to ensure the intensity of material simultaneously, its reason is: these alloying elements can make steel still keep higher intensity under higher tempering temperature condition, but, when the add-on of these alloying elements exceedes certain limit or discontented football association with relational expression, the precipitation of thick carbide can be caused after tempering thus reduce the active strength of material.In addition, what the addition due to alloying element in the inventive solutions compared to that the alloying element addition of steel grade of the prior art will come lacks, and therefore, the alloy content in oil well pipe of the present invention is few, manufacturing cost relatively economical.
Further, the microtexture in High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention is uniform tempered martensite.
Due to H anti-in steel
2the best microtexture state of S stress corrosion performance is tempered martensite, and therefore, the steel with this microtexture can have higher intensity and good sulfur resistance concurrently.
Accordingly, present invention also offers the manufacture method of a kind of production High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe as described above, it comprises step: first smelt and cast, and then makes pipe, and by heating of pipe blank, perforation is rolled into hollow forging; Again after heating, carry out the thermal treatment of quenching+tempering.
In the inventive solutions, the microtexture after quenching-temper is uniform tempered martensite.Improve tempering temperature and be conducive to the Dispersed precipitate of precipitate and the reply of martensite lath, this contributes to the sulfur resistance improving material, but the raising of tempering temperature will inevitably cause the decline of the strength of materials, thus, in order to ensure the mechanical property after material tempering, needing to add appropriate alloying element, specific to this case, making up the reduction of the strength of materials after tempering by adding the alloying elements such as Cr, Mo and V.
Alloying element addition can not exceed certain amount.Due to excessive alloying element can make to organize inherent high tempering after the carbide of separating out based on thick M23C6, thus have a strong impact on the sulfur resistance of material, therefore, technical scheme of the present invention, by the reasonable interpolation of alloying element and the match control of tempering temperature, obtains enough intensity and good sulfur resistance to make material.In addition, uniform tempered martensite microtexture is obtained by the processing parameter controlled in quenching-temper.
Further, in manufacture method of the present invention, be heated to more than Ac3 30 ~ 50 DEG C when quenching and keep 20 ~ 60min, and within≤T second continuous coo1ing to room temperature, wherein T=224*C+54*Mn+65*Cr+95*Mo.
Anti-H in steel
2the best microtexture state of S performance is uniform tempered martensite.Understand the tissues such as generating portion bainite, ferrite when quenching insufficient, this situation can have a strong impact on the sulfur resistance of steel, thus, needs to control the continuous coo1ing temperature in quenching process.Contriver is by analysis of experiments and modeling, and obtain model formation cooling time that this case limits, this model formation have expressed the relation between cooling time and the element of interpolation.
Further, in manufacture method of the present invention, tempering temperature is greater than 670 DEG C.
As described above, anti-H in steel
2the best microtexture state of S performance is uniform tempered martensite.Martensite lath can be made not decompose completely when tempering temperature is lower, this situation also can have a strong impact on the sulfur resistance of steel, therefore, need tempering temperature to be set as >=670 DEG C.
Further, in manufacture method of the present invention, in above-mentioned heating of pipe blank step, by heating of pipe blank to 1050-1250 DEG C, keep 1-3 hour.
Further, in manufacture method of the present invention, in above-mentioned heating steps again, be heated to 900-1000 DEG C, insulation 0.3-1 hour.
High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention is by adding Cr, and Mo and V alloy element, it has higher intensity, good anti-H
2s stress corrosion performance (i.e. sulfur resistance).Yield strength>=the 110Ksi of this oil well pipe, simultaneously its K
1SCCvalue>=30Mpa*m
1/2.
Compare to prior art, the alloy content that High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention adds is few, and ladle refining cost is low, good in economic efficiency.
The hardening capacity of High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention is high, heat treatment step in production technique is simple and easy to control, the tempered martensite microtexture of higher proportion can be obtained in steel, made pipe fitting is applicable to the box cupling preparing large section, wall thickness, also can prepare common specification steel pipe in addition.
Embodiment
To make High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe of the present invention and manufacture method thereof according to specific embodiment below and further illustrating, but specific embodiment and related description do not form the improper restriction for technical scheme of the present invention.
Embodiment A-H and Comparative Examples I-P
The oil well pipe in embodiment A-H and Comparative Examples I-P is manufactured according to following step:
1) smelt and cast, wherein, in smelting process, the percent mass proportioning controlling each chemical element in embodiment A-H and Comparative Examples I-P is as shown in table 1, in castingprocesses, is cast into steel ingot;
2) circular pipe blank is made;
3) heat: by heating of pipe blank to 1050-1250 DEG C, keep 1-3 hour;
4) hollow forging is made after perforated, hot rolling, sizing production process;
5) reheat: be heated to 900-1000 DEG C, insulation 0.3-1 hour;
6) quenching+tempering thermal treatment: be heated to more than Ac3 30 ~ 50 DEG C during quenching and keep 20 ~ 60 minutes, simultaneously within≤T second continuous coo1ing to room temperature, wherein T=224*C+54*Mn+65*Cr+95*Mo, wherein Ac3 can with test determination or with reference to Theresa Andrews (K.W.Andrews) formulae discovery: Ac3=910-203-15.2Ni%+44.7Si%+104V%+31.5Mo%+13.1W% (DEG C); When tempering, tempering temperature is greater than 670 DEG C, and tempering time is 1hr, and concrete processing parameter refers to table 2.
Table 1 lists the percent mass proportioning of each chemical element of each oil well pipe in this case embodiment A-H and Comparative Examples I-P.
Table 1. (wt.%, surplus is Fe and other the inevitable impurity except S, P, O and N)
* note: X1 is relational expression (1), and it is specifically expressed as 0.35Cr+0.85Mo+2.8V, and X2 is relational expression (2), and it is specifically expressed as 2.4Cr+1.1Mo+4.5V.
Table 2 lists the various process parameters of each oil well pipe manufactured in this case embodiment A-H and Comparative Examples I-P.
Table 2.
* note: 1) the continuous room temperature spent time that is cooled to completely of quenching adopts even buried test to carry out.2) T value=224*C+54*Mn+65*Cr+95*Mo
By through each oil well pipe in above-described embodiment A-H and Comparative Examples I-P according to each test mode regulation sampling after and test, thus respectively obtain evaluate its properties testing data row in table 3.Wherein, the performance perameter of yield strength is that the oil well pipe made is processed into API arc sample, obtains by taking the mean after API standard testing, and K
1SCCvalue then obtains according to the test of NACE TM 0177-05 standard D method, and testing circumstance solution A, test temperature is 24 ± 2 DEG C.
Table 3 lists the yield strength parameter of each oil well pipe in this case embodiment A-H and Comparative Examples I-P and anti-H
2s stress corrosion performance parameter.
Table 3.
As can be seen from Table 3, the yield strength Rp0.2 of the oil well pipe of the various embodiments described above A-H all>=792Mpa, and K
1SCCbe worth all>=31.5MPa*m
1/2, the oil well pipe described in embodiment A-H has higher yield strength and good anti-H
2s stress corrosion performance.
Associative list 1, the content of table 2 and table 3 can be found out: when quenching, when continuous coo1ing is lower to the speed of room temperature, can in the tissue of steel the harmful phase such as bainite, thus finally make the sulfur resistance of oil well pipe decline, thus, the K of Comparative Examples I-J
1sccvalue is lower than 30MPa*m
1/2.Because the related chemistry element in comparative example K-M does not meet the constraint condition that relational expression (1) limits, therefore, cause the precipitation strength of steel not enough and cannot more than 670 DEG C during tempering to obtain the high strength of more than 110Ksi.Because the related chemistry element in comparative example N-O does not meet the constraint condition that relational expression (2) limits, so the agglomeration of the precipitate in steel can be caused and oil well pipe cannot be made to obtain higher than 30MPa*m
1/2k
1sccvalue, that is, the sulfur resistance of the oil well pipe of comparative example N-O is on the low side.In addition, the Mn constituent content over range in steel can make to produce obvious banded structure in end product, thus affects the sulfur resistance of steel, thus, and the K of the oil well pipe of comparative example P
1sccvalue is also lower than 30MPa*m
1/2.
Technical scheme of the present invention provides a kind ofly possesses high strength and high anti-H
2the oil well pipe of S stress corrosion performance anti-corrosion capability, its alloy total content <3wt.%, it is especially suitable for containing H
2the exploitation in S deep-seated oil gas field.
It should be noted that above enumerate be only specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar changes thereupon.If all distortion that those skilled in the art directly derives from content disclosed by the invention or associates, protection scope of the present invention all should be belonged to.
Claims (7)
1. a High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe, it is characterized in that, its chemical element percent mass proportioning is: C:0.16 ~ 0.40%, Si:0.1 ~ 0.5%, Mn:0.2% ~ 0.6%, Al:0.01 ~ 0.1%, Nb:0.01 ~ 0.05%, Cr>0.2%, Mo>0.2%, V:0.03 ~ 0.2%, simultaneously mass percentage also demand fulfillment 0.35Cr+0.85Mo+2.8V >=1 of each chemical element, 2.4Cr+1.1Mo+4.5V≤3, surplus is Fe and other inevitable impurity.
2. High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe as claimed in claim 1, it is characterized in that, its microtexture is uniform tempered martensite.
3. the manufacture method of the High-Strength Low-Alloy anti-H 2 S stress corrosion oil well pipe as described in claim 1 ~ 2, is characterized in that, comprise step: smelt and casting, then make pipe, and by heating of pipe blank, perforation is rolled into hollow forging; Again after heating, carry out the thermal treatment of quenching+tempering.
4. manufacture method as claimed in claim 3, is characterized in that, be heated to more than Ac3 30 ~ 50 DEG C and keep 20 ~ 60min during quenching, and within≤T second continuous coo1ing to room temperature, wherein T=224*C+54*Mn+65*Cr+95*Mo.
5. manufacture method as claimed in claim 3, it is characterized in that, tempering temperature is greater than 670 DEG C.
6. manufacture method as claimed in claim 3, is characterized in that, in described heating of pipe blank step, by heating of pipe blank to 1050-1250 DEG C, keeps 1-3 hour.
7. manufacture method as claimed in claim 3, is characterized in that, in described heating steps again, be heated to 900-1000 DEG C, insulation 0.3-1 hour.
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| CN201410766517.1A CN104532132A (en) | 2014-12-11 | 2014-12-11 | High-strength low-alloy oil well pipe for resisting stress corrosion of hydrogen sulfide and manufacture method of high-strength low-alloy oil well pipe |
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| CN107287499A (en) * | 2016-03-31 | 2017-10-24 | 鞍钢股份有限公司 | A kind of high temperature resistant thermal production well oil well pipe and its manufacture method |
| CN108624810A (en) * | 2017-06-26 | 2018-10-09 | 宝山钢铁股份有限公司 | A kind of high sulfur resistive oil well pipe of low-cost high-strength and its manufacturing method |
| CN108779529A (en) * | 2016-03-04 | 2018-11-09 | 新日铁住金株式会社 | Steel and Oil Well Pipe |
| CN110616366A (en) * | 2018-06-20 | 2019-12-27 | 宝山钢铁股份有限公司 | 125ksi steel grade sulfur-resistant oil well pipe and manufacturing method thereof |
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| CN110616366A (en) * | 2018-06-20 | 2019-12-27 | 宝山钢铁股份有限公司 | 125ksi steel grade sulfur-resistant oil well pipe and manufacturing method thereof |
| CN110616366B (en) * | 2018-06-20 | 2021-07-16 | 宝山钢铁股份有限公司 | 125ksi steel grade sulfur-resistant oil well pipe and manufacturing method thereof |
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Application publication date: 20150422 |