CN104846291A - High strength anticorrosion stainless steel, stainless steel oil casing and manufacturing method thereof - Google Patents
High strength anticorrosion stainless steel, stainless steel oil casing and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a high strength anticorrosion stainless steel, which comprises the following chemical elements by mass percentage: less than or equal to 0.1% of C, 0.1-0.5% of Si, 0.1-5% of Mn, 16.5-25.0% of Cr, 8.0-20.0% of Ni, 0.1-5% of Mo, 0.01-0.10% of Al, 0.30-0.45% of Cu, 0.01-0.3% of N, 0.05-0.10% of RE, and the balance Fe and other inevitable impurities. The invention also discloses a stainless steel oil casing made from any stainless steel provided by the invention. The invention additionally discloses a manufacturing method for the stainless steel oil casing. The method comprises the steps of: 1) smelting and casting to obtain a pipe blank; 2) pipe blank heating; 3) pipe making; 4) heat treatment; and 5) cold rolling. The high strength anticorrosion stainless steel and stainless steel oil casing provided by the invention have good CO2 corrosion resistance and acidizing fluid corrosion resistance.
Description
Technical field
The present invention relates to a kind of steel, particularly relate to a kind of stainless steel.The invention still further relates to a kind of tubing and casing to be made up of this stainless steel and manufacture method thereof.
Background technology
Oil pipe is oil, in gas exploitation course for oil or Sweet natural gas are delivered to the pipeline on ground from reservoir, sleeve pipe is positioned at outside oil pipe, and it plays the effect supporting stratum, protection oil pipe.Due to the H often containing high density in reservoir
2s, CO
2, except requiring that oil pipe and sleeve pipe all have except corresponding intensity, impact property, both also requiring, there is certain anti-H
2s/CO
2corrosive nature.In recent years, along with deepening continuously of highly corrosive exploitation of oil-gas field, to the anti-H of oil, sleeve pipe
2s, CO
2corrosive nature creates higher requirement.
Publication number is CN101815802A, publication date is on August 25th, 2010, the oil well seamless tube that the Chinese patent literature that name is called " high strength Cr-Ni alloy material and use its oil well seamless tube " discloses a kind of high strength Cr-Ni alloy material and is made up of this material, in this oil well seamless tube, the mass percentage (wt.) of each chemical element is: below C:0.05%, Si:0.05 ~ 1.0%, Mn:0.01% < Mn < 3.0%, below P:0.05%, below S:0.005%, Cu:0.01 ~ 4%, Ni:25% < Ni < 35%, Cr:20 ~ 30%, Mo:0.01% < Mo < 4.0%, N:0.10 ~ 0.30%, Al:0.03 ~ 0.30%, O (oxygen): less than 0.01%, REM (rare earth element): 0.01 ~ 0.20%, surplus is Fe and other inevitable impurity, and above-mentioned each chemical element meets the condition of following formula (1), formula (1) is N × P/REM≤0.40.
Publication number is JP2290920A, publication date is November 30 nineteen ninety, and the Japanese documentation that name is called " a kind of high strength dual phase stainless steel tube manufacture method " discloses a kind of duplex phase stainless tube, and the mass percentage (wt.%) of its each chemical element is: C:0.01 ~ 0.10%, Si:0.01 ~ 1.0%, Mn:0.3 ~ 1.8%, P≤0.01%, S≤0.003%, Cr 21 ~ 27%, Ni 3 ~ 9%, Mo 2 ~ 4%, N0.1 ~ 0.3%.
Publication number is JP2009068518A, publication date is on October 28th, 2009, name is called that the Japanese documentation of " the high-strength stainless steel steel pipe of a kind of resistance against sulfide stress cracking and high temperature resistance CO2 excellent performance " also discloses a kind of martensite+ferrite diphasic stainless steel steel pipe, the mass percentage (wt.%) of its each chemical element is: C≤0.05%, Si≤1%, Mn≤1%, P≤0.05%, S≤0.002%, Cr:16 ~ 18%, Ni:3 ~ 5%, Mo:2 ~ 3%, Al:0.001 ~ 0.10%, N≤0.05%, its microtexture is martensite+10 ~ 40% ferrite residual austenite below+10%.
Summary of the invention
The object of the present invention is to provide a kind of high-strength corrosion-resistant stainless steel, this stainless intensity is high, and has excellent anti-CO
2corrosive nature and anti-acid corrosion performance.In addition, this high-strength corrosion-resistant stainless steel also possesses excellent welding property.
To achieve these goals, the present invention proposes one and have high-strength corrosion-resistant stainless steel, its chemical element mass percentage content is:
C：≤0.1％，
Si：0.1～0.5％，
Mn：0.1～5％，
Cr：16.5～25.0％，
Ni：8.0-20.0％
Mo：0.1～5％，
Al：0.01～0.10％，
Cu：0.30～0.45％，
N：0.01～0.3％
RE：0.05～0.10％，
Surplus is Fe and other inevitable impurity.
The principle of design of each chemical element in high-strength corrosion-resistant stainless steel of the present invention is:
The interpolation of carbon: C can improve the intensity of steel grade effectively, but the too high alloying element carbide that easily makes of C content is separated out at crystal boundary, causes the appearance of crystal boundary local Cr-depleted region, thus causes the decline of steel grade mechanical property and corrosion resistance.For technical scheme of the present invention, C is relict element, and it should be controlled obtained more low better, but, C content is controlled infinitely low, production cost can be increased widely.Therefore, the C content in high-strength corrosion-resistant stainless steel of the present invention is set as≤0.1wt.%.
Silicon: Si is effective reductor.In order to improve the intensity of steel grade, need to add a certain amount of Si element, but too much Si can cause the reduction of steel toughness, meanwhile, also easily causing the precipitation of the equal harmful second-phase of the σ in steel.Given this, in high-strength corrosion-resistant stainless steel of the present invention, be 0.1wt.% by the lower limit design of Si content, and its upper limit is designed to 0.5wt.%.
Manganese: Mn is austenitic forming element, and it can improve the solubleness of N in steel thus improve steel grade intensity and toughness.In addition, Mn is also effective reductor, and it can play the effect of de-S., too much Mn also can promote the formation of carbide, thus reduces toughness and the erosion resistance of steel grade.For this reason, the content of the Mn in high-strength corrosion-resistant stainless steel of the present invention is set as 0.1 ~ 5wt.%.
Chromium: add anti-local corrosion ability and uniform corrosion ability that Cr can improve steel grade significantly, but, too high Cr will cause the formation of high temperature iron ferritic or the equal harmful second-phase of σ, and the existence of this second-phase will cause the decline of the anti-acid performance of steel grade and anti-SCC performance.Thus, need the Cr content in high-strength corrosion-resistant stainless steel of the present invention to be set as 16.5 ~ 25.0wt.%.
Nickel: Ni is austenitic forming element, and it can improve the anti-SCC performance of steel grade and anti-local corrosion performance, but the Ni of too high amount not only can reduce the work hardening ability of steel grade, also can improve steel grade cost significantly.Therefore, the mass percentage of the Ni in the present invention is controlled to be 8.0 ~ 20.0%.
Molybdenum: Mo can improve steel grade effectively at high Cl
-anti-spot corrosion in environment, anti-crevice corrosion behavior and anti-SCC performance.But Mo is ferrite former, the too much Mo of content will cause the formation of high temperature iron ferritic or the equal harmful second-phase of σ, and the existence of second-phase will cause the decline of steel grade corrosion resistance and anti-SCC performance.Based on technical scheme of the present invention, Mo content should be controlled as 0.1-5.0wt.%.
Aluminium: Al is effective reductor, and it is the alloying element being difficult in steelmaking process avoid.In the inventive solutions, once the content of Al will destroy toughness and the hot workability of steel grade more than 0.10wt.%.Therefore, the Al content in high-strength corrosion-resistant stainless steel of the present invention needs to be set between 0.01 ~ 0.10wt.% scope.
Copper: Xiang Gangzhong adds the corrosion resistance that Cu element contributes to improving steel grade.In addition, Cu is also austenitic forming element.But too high Cu content can reduce the work hardening ability of steel grade.For this reason, the mass percentage of the Cu in high-strength corrosion-resistant stainless steel of the present invention needs control to be 0.30% ~ 0.45%.
The interpolation of nitrogen: N can improve the corrosion resistance of steel grade, and meanwhile, N can also suppress the precipitation of the equal harmful phase of σ.But too high N will cause producing the defects such as pore in ingot casting, meanwhile, also likely cause the precipitation of other harmful phase.So the content of the N in high-strength corrosion-resistant stainless steel of the present invention controls to be 0.01 ~ 0.30wt.%.
The interpolation of rare earth element: RE can improve the toughness of steel grade effectively.For technical scheme of the present invention, when rare earth elements RE content is more than 0.10wt.%, then the welding property of steel grade can be reduced.Thus, in high-strength corrosion-resistant stainless steel of the present invention, the content of rare earth elements RE controls between 0.05% ~ 0.10% scope.
Inevitable impurity element in high-strength corrosion-resistant stainless steel of the present invention is mainly P and S, and these two kinds of impurity elements need to control more low better.
Further, high-strength corrosion-resistant stainless steel of the present invention also has 0 < Nb≤0.1wt%, 0 < V≤0.1wt% and 0 < Ti≤0.1wt% at least one of them.
Nb, V, Ti and C, N have strong binding ability, and Nb, V, Ti can form respective carbide, nitride or carbonitride with C, N, and this compounds contributes to the mechanical property improving steel grade.In addition, Ti can also strengthen the corrosion resistance of steel grade.But, with regard to technical scheme of the present invention, once one of them content of Nb, V, Ti more than 0.1wt.%, the particle of precipitated phase will be made thick, and the oxide inclusion in steel is increased, destroy the intensity of steel on the contrary; Meanwhile, the welding property of steel grade can also be reduced.So the content of Nb, V, Ti in high-strength corrosion-resistant stainless steel of the present invention all must not more than 0.1wt.%.
Further, high-strength corrosion-resistant stainless steel of the present invention also has W:0.01 ~ 2.00%.
W is added with the resistance against sulfide stress cracking performance helping improve steel grade, and meanwhile, W element can also improve the mechanical behavior under high temperature of steel grade effectively.For this reason, the content of the W in high-strength corrosion-resistant stainless steel of the present invention is set as 0.01 ~ 2.00wt.%.
Further preferably, in high-strength corrosion-resistant stainless steel of the present invention, Si element content range is further defined to 0.1 ~ 0.25wt%.
Further preferably, in high-strength corrosion-resistant stainless steel of the present invention, be 0.5 ~ 1.2wt% further by Mn element content range.
Further, the stainless microtexture of high-strength corrosion-resistant of the present invention is homogeneous austenite structure, and minute quantity σ phase and other precipitated phases.
σ phase is that in stainless steel and nickel-base alloy, comparatively common one is harmful to second-phase, is a kind of intermetallic compound, and it exists toughness, ductility and the corrosion resistance that will have a strong impact on alloy.
Compare to Martensite Stainless Steel of the prior art and duplex stainless steel, the high-strength corrosion-resistant stainless steel with above-mentioned microtexture makes steel grade possess high strength and the controlled feature of intensity by precipitation strength and working hardening, meanwhile, varying strength can also be reached to meet different strength demands by the control of postorder cold-rolling process.In addition, the high-strength corrosion-resistant stainless steel with above-mentioned microtexture possesses more excellent corrosion resistance, and it is possessing excellent anti-CO
2while corrosive nature, stainless steel is also made to possess excellent anti-acid corrosion performance.For this reason, owing to having possessed above-mentioned microtexture, the anti-acid performance of the stainless anti-acid Performance Ratio Martensite Stainless Steel of high-strength corrosion-resistant of the present invention and duplex stainless steel has improve more than 10 times.
Further, the grain fineness number of above-mentioned austenite structure is 5-8 level.
Further, above-mentioned σ phase content is lower than 0.5%.
Further, other precipitated phases above-mentioned comprise metallic carbide and high temperature iron ferritic, and the total amount of this precipitated phase is lower than 1%.In the technical program, precipitated phase belongs to harmful phase, therefore needs to control its content.
Another object of the present invention is to provide a kind of stainless steel tubing and casing, this stainless steel tubing and casing has higher intensity, and this stainless steel oil pipe also possesses excellent anti-CO
2corrosive nature and anti-acid corrosion performance.This stainless steel tubing and casing is suitable for oil, Natural gas extraction field.
To achieve these goals, stainless steel tubing and casing of the present invention is obtained by any one high-strength corrosion-resistant stainless steel referred to above.
Correspondingly, present invention also offers the manufacture method of above-mentioned stainless steel tubing and casing, this manufacture method comprises the steps:
(1) smelting and casting obtain pipe;
(2) by heating of pipe blank;
(3) tubulation;
(4) thermal treatment;
(5) cold rolling.
Further, in the manufacture method of stainless steel tubing and casing of the present invention, in above-mentioned steps (3), adopt perforation+hot rolling technology.
Further, in the manufacture method of stainless steel tubing and casing of the present invention, in above-mentioned steps (3), adopt hot extrusion technique.
Further, in the manufacture method of stainless steel tubing and casing of the present invention, in above-mentioned steps (4), adopt the heat treatment mode of solution treatment, to make the microtexture of stainless steel tubing and casing change single solid solution state austenite structure into, and eliminate the harmful second-phase tissue formed in hot procedure early stage.
Further, in the manufacture method of stainless steel tubing and casing of the present invention, the temperature of above-mentioned solution treatment is 980-1200 DEG C.
Further, in the manufacture method of stainless steel tubing and casing of the present invention, in above-mentioned steps (2), more than heating of pipe blank to austenitizing temperature.
High-strength corrosion-resistant stainless steel of the present invention has good corrosion resistance.Especially, this high-strength corrosion-resistant stainless steel has excellent anti-CO
2corrosive nature and anti-acid corrosion performance.Compare to existing Martensite Stainless Steel and duplex stainless steel, the stainless anti-acid performance of this high-strength corrosion-resistant improves more than 10 times.
In addition, high-strength corrosion-resistant stainless steel of the present invention has higher intensity, and strength range covers wide, and its strength range is 80ksi-135ksi.
In addition, high-strength corrosion-resistant stainless steel of the present invention also possesses good welding property.
Stainless steel tubing and casing of the present invention has higher intensity, and its strength range is 80ksi-135ksi, (i.e. 552MPa-965MPa) and this stainless steel tubing and casing has excellent anti-CO
2the comprehensive etch resistant properties such as corrosive nature and anti-acid corrosion performance.
Meanwhile, by the manufacture method of stainless steel tubing and casing of the present invention can produce obtain intensity high, anti-CO
2good, the anti-acid corrosion excellent performance of corrosive nature and the good stainless steel tubing and casing of welding property.
Accompanying drawing explanation
Fig. 1 shows the microtexture of this case embodiment A 6.
Embodiment
Below in conjunction with specific embodiments high-strength corrosion-resistant stainless steel of the present invention, stainless steel tubing and casing and manufacture method thereof are made further explanation, but this explanation and explanation do not form improper restriction to technical scheme of the present invention.
Manufacture the stainless steel tubing and casing in embodiment A 1-A7 according to following step, the percent mass such as content of each chemical element of the stainless steel tubing and casing in embodiment A 1-A7 and the stainless steel tube in comparative example B1 and B2 is as shown in table 1:
(1) smelt: use electric arc furnace or converter+secondary refining process, the proportioning controlling each chemical element is as shown in table 1;
(2) continuous casting obtains pipe;
(3) by heating of pipe blank: use rotary heating furnace by more than heating of pipe blank to austenitizing temperature;
(4) tubulation: adopt perforation+hot rolling technology or hot extrusion technique to form seamless semifinished tube;
(5) thermal treatment: the heat treatment mode adopting solution treatment, the temperature of solution treatment is 980-1200 DEG C, changes single solid solution state austenite structure into and eliminate the second-phase tissue formed in hot procedure early stage to make the microtexture in stainless steel tubing and casing;
(6) cold rolling: to adopt cold deformation mode to make semifinished tube reach desirable strength.
Concrete technology parameter in each step involved by above-mentioned manufacture method is in detail see table 2.
Table 1 lists the mass percentage content of each chemical element made in embodiment A 1-A7 and comparative example B1-B2.
Table 1. (wt.%, surplus is Fe and other inevitable impurity)
| Sequence number | C | Si | Mn | Cr | Ni | Mo | Al | Cu | N | RE | Nb | V | Ti | W |
| A1 | 0.03 | 0.25 | 1.5 | 18.1 | 8.0 | 0.15 | 0.05 | 0.45 | 0.01 | 0.07 | 0.04 | 0.02 | 0 | 0.05 |
| A2 | 0.08 | 0.21 | 5.00 | 22.7 | 20.0 | 4.25 | 0.03 | 0.30 | 0.12 | 0.09 | 0 | 0.03 | 0.01 | 1.20 |
| A3 | 0.02 | 0.15 | 0.28 | 15.9 | 10.2 | 3.14 | 0.01 | 0.40 | 0.07 | 0.05 | 0.04 | 0.01 | 0 | 0.75 |
| A4 | 0.04 | 0.18 | 2.70 | 24.1 | 19.2 | 4.87 | 0.10 | 0.31 | 0.30 | 0.05 | 0.07 | 0 | 0.03 | 1.38 |
| A5 | 0.05 | 0.20 | 3.5 | 19.7 | 15.0 | 2.70 | 0.02 | 0.42 | 0.13 | 0.06 | 0 | 0.02 | 0 | 2.0 |
| A6 | 0.06 | 0.18 | 1.05 | 17.3 | 19.5 | 2.50 | 0.10 | 0.40 | 0.05 | 0.07 | 0 | 0.05 | 0 | 0.17 |
| A7 | 0.09 | 0.20 | 4.95 | 21.4 | 16.7 | 1.84 | 0.01 | 0.37 | 0.09 | 0.09 | 0.05 | 0 | 0.05 | 0.63 |
| B1 | 0.10 | 0.20 | 1.20 | 22.3 | 5.15 | 2.50 | 0.04 | 0.40 | 0.26 | 0.05 | 0.06 | 0 | 0.03 | 1.59 |
| B2* | 0.008 | 0.27 | 0.98 | 13.2 | 5.5 | 2.30 | 0.027 | 0.01 | 0.03 | 0 | 0 | 0 | 0 | 1.0 |
* note: B2 is the stainless steel tube be made up of Martensite Stainless Steel, reaches target strength by quenching+tempering, without the need to cold deformation.
Table 2 lists the processing parameter of the manufacture method of embodiment A 1-A7 and comparative example B1-B2.
Table 2.
* note: B2 is the stainless steel tube be made up of Martensite Stainless Steel, reaches target strength by quenching+tempering, without the need to cold deformation.
After the stainless steel tube sampling of the stainless steel tubing and casing in embodiment A 1-A7 and comparative example B1-B2, carry out V breach charpy impact test at tensile test at room temperature and-10 DEG C, detect the mechanical property obtained and list in table 6.
Use Dynamic Corrosion weight-loss method to the stainless steel tube of the stainless steel tubing and casing in the embodiment A 1-A7 after sampling and comparative example B1-B2, carry out anti-CO
2corrosive nature is tested, and detailed test conditions and solution medium composition are in table 3 and table 4, and test result is listed in table 6.
Use static corrosion weight-loss method to the stainless steel tube to the stainless steel tubing and casing in the embodiment A 1-A7 after sampling and comparative example B1-B2, carry out anti-acid corrosion performance test, detailed test conditions and solution medium composition are shown in as shown in table 5, and test result is listed in table 6.
Table 3 lists anti-CO
2the test conditions of corrosive nature test.
Table 3.
Table 4 lists anti-CO
2the solution medium composition (mg/L) of corrosive nature test.
Table 4.
| 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 |
Table 5 lists the test conditions of anti-acid corrosion performance test.
Table 5.
Table 6 lists every mechanical property parameters of the stainless steel tube of stainless steel tubing and casing in embodiment A 1-A7 and comparative example B1-B2.
Table 6.
As can be seen from Table 6, stainless steel tubing and casing of the present invention has higher intensity and good impelling strength, and its intensity rank reaches 80ksi-135ksi.At anti-CO
2in corrosive nature test, lower than the erosion rate of the stainless steel tube in comparative example B1 and B2, and there is not spot corrosion situation in the erosion rate of the stainless steel tubing and casing in embodiment A 1-A7.In anti-acid corrosion performance test, the erosion rate of the stainless steel tubing and casing in embodiment A 1-A7 is well below the erosion rate of the stainless steel tube in comparative example B1 and B2, simultaneously, there is not spot corrosion situation yet, wherein, the erosion rate of embodiment A 6 is almost only 1/10 of the erosion rate of comparative example B2, and the erosion rate of embodiment A 2 is about 1/84 of the erosion rate of comparative example B1.For this reason, compare to comparative example B1 and B2, the anti-acid corrosion performance of embodiment A 1-A7 is more excellent.
Fig. 1 shows the metallographic structure of embodiment of the present invention A6.As can be seen from the figure, its microtexture is evenly tiny austenite structure, does not almost have σ phase and precipitated phase.
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 (16)
1. a high-strength corrosion-resistant stainless steel, is characterized in that, its chemical element mass percentage content is:
C：≤0.1％，
Si：0.1～0.5％，
Mn：0.1～5％，
Cr：16.5～25.0％，
Ni：8.0～20.0％
Mo：0.1～5％，
Al：0.01～0.10％，
Cu：0.30～0.45％，
N：0.01～0.3％
RE：0.05～0.10％，
Surplus is Fe and other inevitable impurity.
2. high-strength corrosion-resistant stainless steel as claimed in claim 1, is characterized in that also having 0 < Nb≤0.1wt%, 0 < V≤0.1wt% and 0 < Ti≤0.1wt% at least one of them.
3. high-strength corrosion-resistant stainless steel as claimed in claim 1, is characterized in that also having W:0.01 ~ 2.00%.
4. high-strength corrosion-resistant stainless steel as claimed in claim 1, it is characterized in that, Si element content range is 0.1 ~ 0.25wt%.
5. high-strength corrosion-resistant stainless steel as claimed in claim 1, it is characterized in that, Mn element content range is 0.5 ~ 1.2wt%.
6. high-strength corrosion-resistant stainless steel as claimed in claim 1, it is characterized in that, its microtexture is austenite structure, and minute quantity σ phase and precipitated phase.
7. high-strength corrosion-resistant stainless steel as claimed in claim 6, it is characterized in that, the grain fineness number of described austenite structure is 5-8 level.
8. high-strength corrosion-resistant stainless steel as claimed in claim 6, it is characterized in that, described σ phase content is lower than 0.5%.
9. high-strength corrosion-resistant stainless steel as claimed in claim 6, it is characterized in that, described precipitated phase comprises metallic carbide high temperature iron ferritic, and the total amount of described precipitated phase is lower than 1%.
10. adopt stainless steel tubing and casing as obtained in any one high-strength corrosion-resistant stainless steel in claim 1-9.
The manufacture method of 11. stainless steel tubing and casing as claimed in claim 10, is characterized in that, comprise step:
(1) smelting and casting obtain pipe;
(2) by heating of pipe blank;
(3) tubulation;
(4) thermal treatment;
(5) cold rolling.
The manufacture method of 12. stainless steel tubing and casing as claimed in claim 11, is characterized in that, in described step (3), adopt perforation+hot rolling technology.
The manufacture method of 13. stainless steel tubing and casing as claimed in claim 11, is characterized in that, in described step (3), adopt hot extrusion technique.
The manufacture method of 14. stainless steel tubing and casing as claimed in claim 11, is characterized in that, in described step (4), adopts the heat treatment mode of solution treatment.
The manufacture method of 15. stainless steel tubing and casing as claimed in claim 14, is characterized in that, the temperature of described solution treatment is 980-1200 DEG C.
The manufacture method of 16. stainless steel tubing and casing as claimed in claim 11, is characterized in that, in described step (2), more than heating of pipe blank to austenitizing temperature.
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