CN111809121A - Structural function integrated pipeline steel and manufacturing method thereof - Google Patents
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Abstract
The invention belongs to the field of pipeline steel for oil and gas field exploitation, gathering and transportation, and particularly relates to structural and functional integrated pipeline steel and a manufacturing method thereof. The pipeline steel comprises the following chemical components in percentage by weight: 0.02 to 0.08 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 1.0 percent of Mn, 0.5 to 2.0 percent of Cu, less than or equal to 1.0 percent of Al, less than or equal to 0.2 percent of Ce, 1.0 to 2.0 percent of Ni, less than or equal to 0.1 percent of Nb, less than or equal to 0.1 percent of V, less than or equal to 0.1 percent of Ti, less than or equal to 0.005 percent of N, less than or equal to 0.005 percent of S, less than or equal to 0.. According to the invention, through the composite addition of alloy elements such as Cu, Al, Ce, Nb, V, Ti and the like, high-strength and high-toughness indexes with yield strength not lower than 500MPa, tensile strength not lower than 600MPa and impact energy not lower than 180J at-20 ℃ can be obtained. Meanwhile, the pipeline steel also has excellent SSC and HIC resistance and unique microbial corrosion resistance, and realizes structural function integration.
Description
Technical Field
The invention belongs to the field of pipeline steel for oil and gas field exploitation, gathering and transportation, and particularly relates to structural and functional integrated pipeline steel and a manufacturing method thereof.
Background
Pipeline transportation is the premise and the basis of oil and gas exploitation and transportation development and is in the core link of the value chain of the oil and gas industry. With the continuous consumption of the two major energy sources of oil and gas, oil and gas production is being forced to develop towards extreme environments. Accordingly, the selection of the material of the pipeline steel for oil extraction and oil and gas transportation causes a series of problems. Microbial corrosion (MIC) and hydrogen sulfide corrosion (H)2S), including Hydrogen Induced Cracking (HIC) and sulfide stress corrosion cracking (SSC), is a problem to be solved in pipeline steel. How to maintain excellent corrosion resistance (H resistance) on the premise of ensuring high strength and high toughness2S corrosion and MIC corrosion resistance) will have important practical significance for the development of pipeline steel. Therefore, the oil and gas field industry is eagerly hoped to obtain a high-strength, high-toughness and H-resistant oil and gas field2S corrosion and MIC resistance structure function integrated pipeline steel.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a steel sheet having high strength, high toughness and H resistance at the same time2S corrosion and MIC resistance structural function integrated pipeline steel and a manufacturing method thereof.
The technical scheme of the invention is as follows:
the structural and functional integrated pipeline steel comprises the following chemical components in percentage by weight: 0.02-0.08% of C, less than or equal to 0.3% of Si, less than or equal to 1.0% of Mn, 0.5-2.0% of Cu, less than or equal to 1.0% of Al, less than or equal to 0.2% of Ce, 1.0-2.0% of Ni, less than or equal to 0.1% of Nb, less than or equal to 0.1% of V, less than or equal to 0.1% of Ti, less than or equal to 0.005% of N, less than or equal to 0.005% of S, less than or equal to 0.;
according to the weight percentage, the chemical components meet the following requirements:
Cu+Al+Ce≥1.0％ (1)
mass ratio of Ni to Cu Ni/Cu > 0.5 (2)
Wherein, each element symbol in the formulas (1) and (2) is substituted into the corresponding element content.
The structural and functional integrated pipeline steel further comprises one or more than two of Ca, Cr, Mo and B in chemical components, and the weight percentage of each is less than 0.5%.
The manufacturing method of the structure function integrated pipeline steel adopts a blast furnace and external refining mode to smelt and continuously cast a plate blank, or adopts an electric furnace and external refining mode to smelt and continuously cast a plate blank; no matter which method is adopted for smelting and continuous casting, the Ce element needs to be added in the later smelting period, and when the oxygen content (O) and the sulfur content (S) are not more than 0.005 wt%, the Ce element is added, and after the oxygen content (O) and the sulfur content (S) are uniformly stirred, the steel is immediately poured and tapped.
The manufacturing method of the structure-function integrated pipeline steel comprises the steps of rolling continuously cast plate blanks in a controlled manner and cooling in a controlled manner, wherein the initial rolling temperature of rough rolling is 1000-1100 ℃, the final rolling temperature of rough rolling is 900-1000 ℃, the initial rolling temperature of finish rolling is 850-950 ℃, the final rolling temperature of finish rolling is 700-800 ℃, and quick water cooling or slow heap cooling is carried out after finish rolling.
According to the manufacturing method of the pipeline steel with the integrated structure and function, the steel plate which is subjected to rapid water cooling after finish rolling is treated as follows: after finish rolling, cooling with water at a cooling speed of 10-30 ℃/s, wherein the temperature of the water cooling is stopped to be 500-600 ℃, and then carrying out heat preservation, wherein the heat preservation time is the thickness of the steel plate multiplied by the heat preservation time coefficient, the heat preservation time coefficient is 3-6, and the unit of the heat preservation time is as follows: the thickness of the steel plate is given in units of: mm; and after heat preservation, air cooling to room temperature.
According to the manufacturing method of the pipeline steel with the integrated structure and function, the steel plate which is slowly cooled in a heaped mode after finish rolling is processed as follows: and stacking the steel plates after the final rolling together, and air-cooling to room temperature, wherein the stacking height is not less than 1000 mm.
According to the manufacturing method of the pipeline steel with the integrated structure and function, the room-temperature yield strength of the pipeline steel is more than or equal to 500MPa, and the tensile strength of the pipeline steel is more than or equal to 600 MPa; the impact energy of the full-size V-shaped notch is more than or equal to 180J at the temperature of minus 20 ℃.
According to the manufacturing method of the structure-function integrated pipeline steel, the pipeline steel has excellent SSC resistance, and does not break after 720 hours under the constant load of 80% yield strength by referring to NACE TM0177 standard, method dA, A solution.
According to the manufacturing method of the pipeline steel with the integrated structure and function, the pipeline steel has excellent HIC (hydrogen induced cracking) resistance, referring to NACE (national association model) TM0284 standard, solution A is selected, and hydrogen induced cracking parameters are as follows after the pipeline steel is soaked for 96 hours: the crack sensitivity rate CSR, crack length rate CLR and crack thickness rate CTR are zero.
According to the manufacturing method of the pipeline steel with the integrated structure and function, the pipeline steel has unique MIC resistance, and the depth of a pitting pit is less than 3 mu m within 21 days of soaking in oil gas produced water containing Sulfate Reducing Bacteria (SRB).
The design idea of the invention is as follows:
cu, Nb, V and Ti in the steel not only have precipitation strengthening effect, but also have beneficial hydrogen trapping effect, and Cu in the steel also has microbial corrosion resistance. The composite addition of Cu, Al and Ce can play a synergistic role, can effectively prevent H from entering steel, can inhibit the formation of bacterial biofilms and plays a role in resisting microbial corrosion. Cu, Al, Ce, Nb, V and Ti are added in a compounding way, and the excellent comprehensive performance pipeline steel with high strength, high toughness, SSC and HIC resistance and MIC resistance can be obtained.
The contents of main elements in the present invention are explained as follows:
in the component design of the structure function integrated pipeline steel, copper (Cu), aluminum (Al) and cerium (Ce) are the most key alloying elements in the steel, and the purpose of the invention can be achieved only by the composite addition of the copper (Cu), the aluminum (Al) and the cerium (Ce).
Copper (Cu): cu is an austenite forming element in steel, has a small solubility in ferrite, and has a sharp decrease in solubility with a decrease in temperature, and is hardly soluble in α -Fe at room temperature. Therefore, after aging treatment, Cu is precipitated in the form of a second phase, thereby strengthening the steel. The addition of Cu can promote the formation of a steel surface protective film and reduce the entering of H atoms into a steel matrix, and a nano-sized Cu-rich phase precipitated in the aging process can capture hydrogen to serve as a beneficial hydrogen trap effect. Both of these effects of Cu in steel can greatly reduce the deleterious effects of H on steel. The Cu in the steel also has the microbial corrosion resistance, when the Cu content is lower, the Cu-rich phase precipitated in the matrix is insufficient, and the microbial corrosion resistance is lower; when the Cu content is relatively excessively high, impact toughness and hot workability are adversely affected. Comprehensively, the Cu content in the invention is 0.5-2.0 wt%.
Aluminum (Al): al is an effective alloy element for deoxidation in steel, so that the Al has very strong bonding force with oxygen (O), and an alumina film layer is very stable and compact, so that the Al has good capability of hindering hydrogen (H) diffusion. The pipeline steel of the invention is added with not more than 1.0 wt% of Al from H2The source of S corrosion is considered, namely, Al in the steel is fully utilized to form an oxide film to block the entering of H, the content of H in the steel is reduced, the possibility of SSC is effectively reduced, and the nano-sized Cu-rich phase and Ce in the steel have the effect of beneficial hydrogen traps, so that the excellent SSC resistance is achieved. In view of the above, the content of Al in the present invention is preferably in the range of 0.1 to 0.6 wt%.
Cerium (Ce): rare earth elements in steel are called "industrial vitamins". The addition of a proper amount of rare earth into the steel has multiple beneficial effects, such as purification of molten steel, optimization of grain boundary, reduction of corrosion source, and improvement of toughness and uniform corrosion resistance of the steel; the rare earth steel can also refine crystal grains and capture H atoms, thereby improving the obdurability of the steel and reducing the hydrogen embrittlement sensitivity; moreover, the rare earth element Ce can interact with the outer surface of the bacterial cell membrane and replace metal elements which have important functions in the life process of bacteria, so that the life process of the bacteria is influenced, and the antibacterial effect is achieved. The rare earth Ce, Cu and Al are added to generate a synergistic effect, so that a more excellent effect can be exerted. Comprehensively, the content of the rare earth Ce in the invention is less than or equal to 0.2 wt%, and the preferable range is 0.1-0.2 wt%.
Nickel (Ni): ni is an element for effectively improving the toughness of steel, and can inhibit the hot brittleness of Cu in the steel, but the action needs to meet the requirement that the mass ratio of Ni and Cu is not less than 0.5, and the content of Ni is too high, so that the cost is increased. Comprehensively considered, the Ni content in the pipeline steel is 1.0-2.0 wt%.
Preferably, the chemical compositions of Cu, Al and Ce meet the following requirements: 1.5 percent of Cu, Al and Ce is more than or equal to 2.5 percent; meanwhile, the chemical compositions of Ni and Cu meet the following requirements: the mass ratio of Ni to Cu is more than or equal to 0.5 and less than or equal to 2.0.
The pipeline steel of the invention specifies that the content of N is less than or equal to 0.005 wt%. Excess N readily combines with Al in the steel to produce large-sized AlN, thereby affecting SSC resistance, HIC resistance and impact toughness.
The content of O and S in the pipeline steel is regulated to be less than or equal to 0.005 wt%. Rare earth Ce has the characteristic of strong chemical activity, O, S inclusion is easy to form, if the contents of O and S are too high, the yield of Ce is influenced, large-size inclusion is formed, and not only can Ce not play a role, but also corrosion resistance and impact toughness are deteriorated.
The invention has the advantages and beneficial effects that:
1. according to the invention, through the composite addition of alloy elements such as Cu, Al, Ce, Nb, V, Ti and the like, high-strength and high-toughness indexes with yield strength not lower than 500MPa, tensile strength not lower than 600MPa and impact energy not lower than 180J at-20 ℃ can be obtained. Meanwhile, the pipeline steel also has excellent SSC and HIC resistance and unique microbial corrosion resistance, and realizes structural function integration.
2. The invention overcomes the defects of strength, toughness and H resistance of steel2S corrosion Performance this trade-off relationship takes into account MIC resistance. Thus, the method is suitable for geological conditions with complex working conditions and contains hydrogen sulfide (H)2S), corrosive microorganisms and the like under severe environments, and has the characteristics of high strength, high toughness, Hydrogen Induced Cracking (HIC) resistance, sulfide stress corrosion cracking (SSC) resistance, microbial corrosion resistance (MIC) resistance and the like.
Drawings
FIG. 1 is a graph showing the morphology of the oxide film on the surface of the steel of example 3.
FIG. 2 is a topographical map of nanometer-sized hydrogen traps precipitated in the tissue of example 1.
FIG. 3 is a topographical map of the pit of example 2 incubated at 500 ℃.
FIG. 4 is a topographical map of pitting pits for comparative example 1 incubated at 550 ℃.
Detailed Description
In the specific implementation process, the manufacturing method of the pipeline steel comprises the following steps:
(1) according to the invention, the raw materials are mixed according to the chemical components, the smelting of pipeline steel is carried out in a smelting mode of blast furnace and external refining, the Ce element is added after the oxygen content (O) and the sulfur content (S) are not more than 0.005 wt%, and the mixture is uniformly stirred and continuously cast;
(2) and (3) performing controlled rolling on the continuous casting billet, wherein the initial rolling temperature of rough rolling is 1080 ℃, the final rolling temperature of rough rolling is 980 ℃, the initial rolling temperature of finish rolling is 900 ℃, and the final rolling temperature of finish rolling is 730 ℃.
(3) Rapidly cooling the steel plate (22.8mm) after final rolling at a water cooling speed of 23 ℃/s and final cooling temperatures of 500 ℃, 550 and 600 ℃ respectively, then respectively carrying out heat preservation, wherein the heat preservation time coefficient is 6, the heat preservation time is 138 minutes, and carrying out air cooling to room temperature after the heat preservation is finished; wherein the heat preservation time of the steel plate is 3-6 minutes/mm, and the heat preservation coefficient is 3-6.
The prepared steel plate is subjected to mechanical property test according to national standards, the tensile property test temperature is room temperature, the size of an impact sample is 10mm multiplied by 55mm, a V-shaped notch is formed, and the test temperature is-20 ℃.
The pitting caused by MIC is considered as the greatest damage to the material, and the pitting depth is considered as an important index for quantitatively evaluating the MIC resistance of the material. The method evaluates the quality of MIC resistance by the maximum pit depth of the surface of the material.
The prepared sample blocks of each example and each comparative example are soaked in oil gas produced water containing SRB for 21 days, and the maximum pitting depth of the surface of the sample after corrosion, which is caused by SRB corrosion, is detected by a laser confocal microscope.
Evaluation of SSC resistance the SSC resistance was evaluated according to NACE TM0177 standard, Methoda, solution A, constant load loading 80% yield strength.
And (4) evaluating the HIC resistance according to NACE TM0284 standard, selecting solution A, soaking for 96 hours, and detecting hydrogen induced cracking parameters (crack sensitivity rate CSR, crack length rate CLR and crack thickness rate CTR).
Hereinafter, the present invention will be described by comparing various examples and comparative examples, which are for illustrative purposes only and the present invention is not limited to these examples.
Example 1
The pipeline steel comprises the following chemical components in percentage by weight: 0.029% of C, 0.19% of Si, 0.59% of Mn, 1.35% of Cu, 0.35% of Al, 0.15% of Ce, 1.05% of Ni, 0.01% of Mo, 0.019% of Nb, 0.017% of Ti, 0.003% of N, 0.001% of S, 0.002% of P, 0.002% of O, 0.005% of Ca and the balance of Fe. Wherein, Cu + Al + Ce is 1.85%, Ni/Cu is 0.78%.
Example 2
The pipeline steel comprises the following chemical components in percentage by weight: 0.027% of C, 0.19% of Si, 0.56% of Mn, 1.82% of Cu, 0.25% of Al, 0.15% of Ce, 1.03% of Ni, 0.03% of Cr, 0.018% of Nb, 0.005% of V, 0.002% of Ti, 0.004% of N, 0.001% of S, 0.002% of P, 0.003% of O, 0.005% of Ca, 0.0005% of B and the balance of Fe. Wherein, Cu + Al + Ce is 2.22%, Ni/Cu is 0.57%.
Example 3
The pipeline steel comprises the following chemical components in percentage by weight: 0.033% of C, 0.20% of Si, 0.59% of Mn, 1.83% of Cu, 0.45% of Al, 0.10% of Ce, 1.94% of Ni, 0.01% of Mo, 0.017% of Nb, 0.015% of Ti, 0.004% of N, 0.001% of S, 0.002% of P, 0.003% of O, 0.005% of Ca and the balance of Fe. Wherein, Cu + Al + Ce is 2.33%, Ni/Cu is 1.06.
Comparative example 1
The pipeline steel comprises the following chemical components in percentage by weight: 0.028% of C, 0.18% of Si, 0.59% of Mn, 0.01% of Cu0.01%, 0.04% of Al, 0.10% of Ni, 0.03% of Cr, 0.02% of Nb, 0.01% of V, 0.01% of Ti, 0.004% of N, 0.02% of S, 0.03% of P, 0.05% of O and the balance of Fe. Wherein, Cu + Al + Ce is 0.05%, Ni/Cu is 10%.
TABLE 1 correlation of holding temperatures of the examples and comparative steels with respect to their corresponding properties
The results of the examples show that the yield strength at room temperature of the pipeline steel is not lower than 500MPa, and the tensile strength is not lower than 600 MPa; the impact energy of the full-size V-shaped notch is more than or equal to 180J at the temperature of minus 20 ℃. Preferably, the room temperature yield strength of the pipeline steel is more than or equal to 600MPa, and the tensile strength is more than or equal to 700 MPa; the impact energy of the full-size V-shaped notch is more than or equal to 180J at the temperature of minus 20 ℃.
The pipeline steel has excellent SSC resistance, and does not break for 720 hours under the constant load of 80% yield strength by referring to NACE TM0177 standard Methoda, A solution. This is mainly due to the formation of dense alumina oxide films on the surface of the material and the formation of beneficially nano-sized hydrogen traps within the tissue, see fig. 1 and 2.
The pipeline steel has excellent HIC resistance, and selects the solution A according to NACE TM0284 standard, and after the pipeline steel is soaked for 96 hours, the hydrogen induced cracking parameters (the crack sensitivity rate CSR, the crack length rate CLR and the crack thickness rate CTR) are all zero.
The pipeline steel also has unique MIC resistance, and the depth of a pitting pit is less than 3 mu m after the pipeline steel is soaked in oil gas produced water containing SRB for 21 days, which is shown in attached figures 3 and 4.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The structural-function integrated pipeline steel is characterized by comprising the following chemical components in percentage by weight: 0.02-0.08% of C, less than or equal to 0.3% of Si, less than or equal to 1.0% of Mn, 0.5-2.0% of Cu, less than or equal to 1.0% of Al, less than or equal to 0.2% of Ce, 1.0-2.0% of Ni, less than or equal to 0.1% of Nb, less than or equal to 0.1% of V, less than or equal to 0.1% of Ti, less than or equal to 0.005% of N, less than or equal to 0.005% of S, less than or equal to 0.;
according to the weight percentage, the chemical components meet the following requirements:
Cu+Al+Ce≥1.0％ (1)
mass ratio of Ni to Cu Ni/Cu > 0.5 (2)
Wherein, each element symbol in the formulas (1) and (2) is substituted into the corresponding element content.
2. The structurally and functionally integrated line steel as claimed in claim 1, wherein the line steel further comprises one or more of Ca, Cr, Mo and B in a weight percentage of < 0.5%.
3. A manufacturing method of the structural-functional integrated pipeline steel of claim 1, characterized in that a slab is smelted and continuously cast by adopting a blast furnace + external refining mode, or a slab is smelted and continuously cast by adopting an electric furnace + external refining mode; no matter which method is adopted for smelting and continuous casting, the Ce element needs to be added in the later smelting period, and when the oxygen content (O) and the sulfur content (S) are not more than 0.005 wt%, the Ce element is added, and after the oxygen content (O) and the sulfur content (S) are uniformly stirred, the steel is immediately poured and tapped.
4. The method for manufacturing the structure-function integrated pipeline steel according to claim 3, wherein the continuous cast slab is subjected to controlled rolling and controlled cooling, the rough rolling start temperature is 1000-1100 ℃, the rough rolling finish rolling temperature is 900-1000 ℃, the finish rolling start temperature is 850-950 ℃, the finish rolling temperature is 700-800 ℃, and the rapid water cooling or slow heap cooling is performed after finish rolling.
5. The method for manufacturing the structure-function integrated pipeline steel according to claim 4, wherein the steel plate which is rapidly water-cooled after finish rolling is subjected to the following treatment: after finish rolling, cooling with water at a cooling speed of 10-30 ℃/s, wherein the temperature of the water cooling is stopped to be 500-600 ℃, and then carrying out heat preservation, wherein the heat preservation time is the thickness of the steel plate multiplied by the heat preservation time coefficient, the heat preservation time coefficient is 3-6, and the unit of the heat preservation time is as follows: the thickness of the steel plate is given in units of: mm; and after heat preservation, air cooling to room temperature.
6. The method for manufacturing the structure-function integrated pipeline steel according to claim 4, wherein the steel plate which is slowly cooled in heap after finish rolling is subjected to the following treatment: and stacking the steel plates after the final rolling together, and air-cooling to room temperature, wherein the stacking height is not less than 1000 mm.
7. The manufacturing method of the structure-function integrated pipeline steel as claimed in claim 4, wherein the room temperature yield strength of the pipeline steel is not less than 500MPa, and the tensile strength is not less than 600 MPa; the impact energy of the full-size V-shaped notch is more than or equal to 180J at the temperature of minus 20 ℃.
8. The method for manufacturing a structurally and functionally integrated pipeline steel according to claim 4, wherein the pipeline steel has excellent SSC resistance, and does not break at a constant load of 80% yield strength for 720 hours according to NACE TM0177 standard, Methoda, solution A.
9. The method for manufacturing the structure-function integrated pipeline steel according to claim 4, wherein the pipeline steel has excellent HIC resistance, and the solution A is selected according to NACE TM0284 standard, and hydrogen induced cracking parameter is determined after soaking for 96 hours: the crack sensitivity rate CSR, crack length rate CLR and crack thickness rate CTR are zero.
10. The method for manufacturing the structure-function integrated pipeline steel according to claim 4, wherein the pipeline steel has unique MIC resistance, and the pitting depth is less than 3 μm within 21 days of soaking in oil gas produced water containing Sulfate Reducing Bacteria (SRB).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449698A (en) * | 2022-09-30 | 2022-12-09 | 马鞍山钢铁股份有限公司 | Microbial corrosion resistant pipeline steel with yield strength of 480MPa and preparation method thereof |
| CN115679218A (en) * | 2022-11-14 | 2023-02-03 | 鞍钢股份有限公司 | Steel for refining pipeline in coastal atmospheric environment and corrosion evaluation method thereof |
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| CN115679218A (en) * | 2022-11-14 | 2023-02-03 | 鞍钢股份有限公司 | Steel for refining pipeline in coastal atmospheric environment and corrosion evaluation method thereof |
| CN115717214A (en) * | 2022-11-14 | 2023-02-28 | 鞍钢股份有限公司 | Steel for refining pipeline in coastal atmospheric environment and preparation method thereof |
| CN115679218B (en) * | 2022-11-14 | 2023-11-10 | 鞍钢股份有限公司 | Steel for coastal atmospheric environment refining pipeline and corrosion evaluation method thereof |
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