CN107400835B - Steel resistant to corrosion of sulfate reducing bacteria, application and preparation method thereof - Google Patents
Steel resistant to corrosion of sulfate reducing bacteria, application and preparation method thereof Download PDFInfo
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C21D1/26—Methods of annealing
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
Abstract
The invention discloses a steel for resisting sulfate reducing bacteria corrosion, an application and a preparation method thereof, wherein the steel comprises the following main chemical components in percentage by weight: c is less than or equal to 0.04 percent; si: 0.1-0.5%; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.15 to 1.5 percent; al: 1.5-3.5%; ce: 0.01 to 0.1 percent. The balance of Fe and inevitable impurities. The method for manufacturing the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following steps: mixing the raw materials, smelting, casting and forming to obtain a final product component; and then carrying out high-temperature annealing heat treatment, wherein the heating temperature is 1150-1250 ℃, and the heat preservation time is 60-120 minutes. The steel manufactured by the invention can effectively resist the corrosion of SRB in the external environment, has the yield strength of more than 380MPa, meets the requirement of J55 steel grade, and can well meet the problem of premature failure of a pipe for oil extraction of a water injection well due to the corrosion of the SRB.
Description
Technical Field
The invention relates to stainless steel and a preparation method thereof, in particular to steel for bacterial corrosion resistance and a preparation method thereof, which are applied to the technical field of steel for fossil energy exploration, exploitation and conveying pipelines and other sulfate reducing bacteria corrosion resistant process parts.
Background
High pour-point oil reservoirs are widely distributed in the world and have abundant geological reserves. The oil fields of Liaohe, Jilin, Dagang, Henan and the like in China all have high-pour-point oil reservoirs with considerable reserves, and the common characteristics of high wax content and high freezing point are that the oil reservoirs are high in wax content and high in freezing point. Because the high pour-point oil reservoir has special properties, the ultimate recovery rate of the oil reservoir can be effectively improved by injecting normal-temperature water for development. Because of the long-term large amount of water injection, a low-temperature zone is formed around the water injection well, and the conditions of temperature, oxygen deficiency and the like are very suitable for the growth and the propagation of bacteria. And because the injected water is continuously brought into nutrient substances, the mass propagation of harmful Bacteria such as sulfate-Reducing Bacteria (SRB) and the like becomes possible.
SRB corrodes subterranean oil well pipes, causing them to be damaged by perforation corrosion. If the water injection well casing of a certain oil field is used for 1 month in a well, the steel pipe is corroded and perforated, and the SRB content is up to 5000-10000 per ml through detection. The corrosion of sulfate reducing bacteria is mainly caused by the action of hydrogenase, and the mechanism of causing metal corrosion is divided into two steps: the first step is that the bacteria release atomic hydrogen from the metal surface by hydrogenase and help the hydrogen atoms to reduce sulfate to sulfide; the second step is cathodic depolarization. Corrosion of SRB is therefore essentially a problem of galvanic corrosion.
Currently, the antibacterial steel produced at home and abroad mainly aims at strains such as escherichia coli, staphylococcus aureus and the like. For example, chinese patent CN200510013238.9 relates to an austenitic antibacterial stainless steel, which comprises the following chemical components in percentage by weight (wt%): c: 0.03-0.15, Cr: 11-15, Ni: 1.0-3.5, Mn: 7.0-15.0, N: 0.06-0.3, Cu: 1.0-3.0, Ag: 0.01-0.1, Nb: 0-0.10, S is less than or equal to 0.02, P is less than or equal to 0.03, Si: 0.1-1, the balance being Fe, see Table 1; for another example, the ferrite antibacterial stainless steel disclosed in chinese patent CN02144568.0 has chemical components of C less than or equal to 0.2%, Si less than or equal to 3%, Mn less than or equal to 2%, Cr: 10-30%, Cu: 0.4-2.2%, Zn < 1%, and the balance Fe and inevitable impurities, see Table 1. The antibacterial mechanism of the antibacterial steel mainly depends on epsilon-Cu or Ag precipitation phase, and the antibacterial steel has lasting antibacterial performance, wide antibacterial range and good mechanical performance and corrosion resistance.
Since the corrosion of SRB bacteria is characterized by electrochemical corrosion, it is one of effective measures to increase the electrode potential of steel materials in order to improve the electrochemical corrosion performance of the materials. From this perspective, patent CN201210211075.5 starts with Cr: 8.5 to 25 percent; cu: 0.15 to 2.5 percent; al: 0.5-3.5% of chemical components, and the better effect is obtained, see table 1. However, sulfate reducing bacteria are not easily found in flowing fluids, but rather are attached to the pipe in clusters or colonies. It is therefore difficult to remove it completely by using a biocide once it is present. Reports on steels effective against SRB corrosion have not been found.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide steel for resisting corrosion of sulfate reducing bacteria, application and a preparation method thereof. In order to solve the corrosion problem of an oil well pipe caused by mass propagation of Sulfate Reducing Bacteria (SRB) in a secondary oil extraction and water injection system along with the development of an oil field, because the SRB is corroded by microorganisms, bacteria are adsorbed on the surface of metal and form a biological film, a flexible oxide film is formed on the surface of the metal in the production process to block the adsorption of the SRB on the surface of the metal and the electrochemical process of the SRB, so that the corrosion problem of the SRB is effectively solved; on the other hand, considering that the damage of the oxide film can cause the corrosion of the SRB to the material, the antibacterial alloy element is adopted for alloy design, and the electrochemical corrosion resistance of the material is improved. The invention aims to provide steel capable of effectively resisting SRB corrosion and a production method of a petroleum pipe so as to meet the corrosion resistance requirement of the SRB corrosion of a water injection well on materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the steel for resisting the corrosion of sulfate reducing bacteria comprises the following main chemical components in percentage by weight: c is less than or equal to 0.04 percent; si: 0.1 to 0.5 percent; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.15 to 1.5 percent; al: 1.5-3.5%; ce: 0.01-0.1%; the balance of Fe and inevitable impurities.
In the chemical components of the steel for preferably resisting the corrosion of the sulfate reducing bacteria, the weight percentage of C: 0.01-0.04%; mn: 0.3 to 0.5 percent.
In the further preferable chemical composition of the steel for corrosion resistance to sulfate reducing bacteria, the ratio of Si: 0.2 to 0.5 percent; cu: 0.98-1.5%; ce: 0.02-0.07%.
In a further preferred chemical composition of the steel for corrosion resistance to sulfate-reducing bacteria, Cr: 16 to 18.1 percent; al: 2.4-3.5%; ce: 0.02-0.05%.
As a further preferable technical scheme of the scheme, the chemical components of the alloy further comprise at least any two of Mo less than or equal to 0.6 wt%, V less than or equal to 0.15 wt%, Ti less than or equal to 0.05 wt% and Nb less than or equal to 0.05 wt% in percentage by weight. In the chemical composition of the further preferable steel for resisting the corrosion of the sulfate reducing bacteria, the ratio of Mo: 0.2-0.6%, V: 0.06-0.15%; ti: 0.03 to 0.05 percent. In a still more preferred chemical composition of the steel for corrosion resistance to sulfate-reducing bacteria, Mo: 0.3 to 0.6 percent.
The invention relates to an application of steel for resisting corrosion of sulfate reducing bacteria, which is used as steel for oil well pipes of oil and gas wells.
The invention relates to a preparation method of steel for resisting corrosion of sulfate reducing bacteria, which comprises the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c is less than or equal to 0.04 percent; si: 0.1-0.5%; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.15 to 1.5 percent; al: 1.5-3.5%; ce: 0.01-0.1%; the balance of Fe and inevitable impurities; mixing the chemical components, smelting, and then directly performing continuous casting to form an alloy steel primary blank, or adopting a method combining casting and later-stage pressure processing to firstly prepare an alloy steel ingot by a casting process and then rolling to prepare an alloy steel primary blank;
b. heating the alloy steel primary blank prepared in the step a to 1200-1300 ℃, and then carrying out hot rolling to form a product component; when hot rolling is carried out, the hot rolling temperature is preferably controlled to be 1200-1270 ℃;
c. and c, carrying out high-temperature annealing heat treatment on the product component prepared in the step b, controlling the heating temperature to 1150-1250 ℃, and keeping the temperature for 60-120 minutes. When high-temperature annealing heat treatment is carried out, the heating temperature is preferably controlled to be 1200-1250 ℃, the heat preservation time is preferably 60-90 minutes, and finally the annealed product component is cooled along with the furnace, namely an oxide film is generated on the surface of the material of the steel for resisting the corrosion of the sulfate reducing bacteria. The invention adopts a high-temperature annealing heat treatment production process system to carry out final heat treatment on the product member, and after the product member is cooled along with a furnace, a compact oxide film with the average thickness of less than 60 mu m is generated on the surface of the steel prepared by the invention.
The following are the action principles and specific descriptions of the chemical components of the steel for resisting the corrosion of the sulfate reducing bacteria:
c: the strength of the steel can be effectively improved, but the content is too high, so that an oxide film is loosened and falls off, and the reduction shows that the quality of the oxide film is not more than 0.04 percent by weight.
Si: the solid solution is dissolved in ferrite to improve the yield strength of steel, but the plasticity and the toughness are lost at the same time, and the passivation capability of the steel can be effectively improved, so that the corrosion resistance of the steel is improved, and the content of silicon is preferably 0.1-0.5% by weight percent.
Mn: mainly dissolves in ferrite to play a role in strengthening, but segregation is serious when the content is too high, the SRB corrosion performance is reduced, and the Mn content is preferably less than or equal to 0.5 percent according to weight percentage.
Cr: effectively improves the SRB corrosion resistance of the steel. Cr obviously improves the electrode potential of steel, the molar ratio of Cr follows n/8 rule, and Cr is formed at high temperature2O3The film can effectively block the adhesion of the SRB, and meanwhile, Cr has toxicity to the SRB and is not beneficial to the growth of the SRB. When the Cr content is less than 16%, the quality of the formed oxide film is poor. However, the cost is increased due to the high Cr content, and the Cr content is preferably 16-24% by weight.
Cu: the strength of the steel is improved, the SRB corrosion resistance of the steel is effectively improved, but the Cu brittleness phenomenon of the steel can occur when the content is too high, and the content is preferably 0.15-1.5% by weight.
Al: the deoxidizing nitrogen-fixing element can effectively improve the passivation capability of steel, the corrosion resistance of the steel, the quality of an oxide film and the SRB corrosion resistance of the steel, and the steel brittleness is increased when the content is too high, and the content is preferably 1.5-3.5% by weight.
Ce: effectively block the diffusion process of ions in the oxide film and obviously improve Cr2O3/Al2O3The toughness of the composite oxide film is high in cost when the content of the single oxide film is high, so that the weight is heavyThe amount of the additive is preferably 0.01-0.1%.
Mo: the tempering stability of the steel is improved, the strength and the pitting corrosion resistance of the steel are improved, and the steel has satisfactory corrosion resistance. The cost is high when the content is high, and the content is preferably less than or equal to 0.6 percent according to weight percentage.
V: strong carbonitride forming elements are used to adjust the strength of the steel. If the content is too high, the cost is too high, and the content is preferably less than or equal to 0.15 percent by weight.
Ti: strong carbonitride forming elements for adjusting the strength of the steel; if the content is too high, coarse TiN is easily formed. The content is preferably less than or equal to 0.05 percent by weight.
Nb: strong carbonitride forming elements, which effectively regulate the strength of the steel. If the content is too high, the cost is too high, and the content is preferably less than or equal to 0.05 percent by weight percent.
The mechanism of the alloy design of the invention is as follows:
1) cr with moderate thickness is generated in the production process by adding Cr and Al2O3/Al2O3The Ce is added to the composite oxide film to improve the toughness of the oxide film, so that the oxide film generated on the surface of the steel is compact and has strong adhesion, and the corrosion of the SRB is blocked;
2) cr and Al are added, the electrode potential of the steel is improved, and the SRB electrochemical corrosion resistance is improved;
3) elements such as Cr, Cu and the like are added, and the toxicity of the elements on the SRB is utilized to inhibit the reproduction and growth of the SRB;
4) and alloy elements such as Mo, Nb, V, Ti and the like are added, so that the steel grade reaches a proper strength level.
The method for manufacturing the steel and the petroleum pipe comprises the following steps: the molten steel with the chemical components is smelted and then continuously cast into a round billet, or cast into a square billet and then rolled into a round billet. After heating to 1250 +/-50 ℃, hot rolling, and adopting a high-temperature annealing heat treatment production process system for the obtained steel or seamless steel pipe, wherein the heating temperature is as follows: 1150-1250 ℃, heat preservation time: and cooling the substrate along with the furnace for 60-120 minutes, wherein the average thickness of the oxide film generated on the surface is less than 60 mu m.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. according to the invention, a heat treatment production process system of high-temperature annealing is adopted, on one hand, the thickness of the oxide film formed at high temperature is proper, and the stress generated in the cooling process can be effectively eliminated during tempering; on the other hand, the segregation structure can be eliminated at high temperature, so that the components are homogenized, and a diffuse, uniform and fine second phase is precipitated during subsequent cooling to achieve the effect of a strengthened matrix; the heat treatment system can ensure that an oxide film with good SRB resistance can be obtained while excellent mechanical property is obtained;
2. the SRB-resistant steel obtained by the component design and the process thereof and the oil well pipe made of the SRB-resistant steel have excellent mechanical properties, can effectively resist SRB corrosion of the external environment, and can well meet the requirement of the water injection well on the harsh environment of an oil extraction pipe.
Drawings
FIG. 1 is a photomicrograph of an oxide film formed on the surface of a steel for corrosion resistance against sulfate-reducing bacteria according to example one of the present invention.
FIG. 2 is a microscopic photograph of the cross-sectional morphology of the oxide film on the surface of the steel for corrosion resistance to sulfate-reducing bacteria prepared in the first embodiment of the present invention.
FIG. 3 is a photograph showing the deformation of the oxide film formed on the surface of the steel for corrosion resistance against sulfate-reducing bacteria according to the first embodiment of the present invention.
FIG. 4 is a photograph showing the surface of the steel for corrosion resistance against sulfate-reducing bacteria according to the comparative example of the present invention after the deformation of the oxide film formed thereon.
Detailed Description
The preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, the steel for corrosion resistance to sulfate-reducing bacteria comprises the following main chemical components in percentage by weight: c: 0.02 percent; si: 0.1 percent; mn: 0.3 percent; cr: 20.5 percent; cu: 0.15 percent; al: 3.1 percent; ce: 0.1 percent; v: 0.15 percent; nb: 0.05 percent; the balance of Fe and inevitable impurities.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.02 percent; si: 0.1 percent; mn: 0.3 percent; cr: 20.5 percent; cu: 0.15 percent; al: 3.1 percent; ce: 0.1 percent; v: 0.15 percent; nb: 0.05 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and rolling to prepare an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1300 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, performing high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to 1250 ℃ and the heat preservation time to 120 minutes, and generating an oxide film with the average thickness of 25 mu m on the surface of the seamless steel pipe, wherein the oxide film is shown in figures 1 and 2.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, the steel for corrosion resistance to sulfate-reducing bacteria comprises the following main chemical components in percentage by weight: c: 0.01 percent; si: 0.2 percent; mn: 0.3 percent; cr: 18.1 percent; cu: 0.98 percent; al: 2.4 percent; ce: 0.02 percent; mo: 0.3 percent; v: 0.07 percent; the balance of Fe and inevitable impurities.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.01 percent; si: 0.2 percent; mn: 0.3 percent; cr: 18.1 percent; cu: 0.98 percent; al: 2.4 percent; ce: 0.02 percent; mo: 0.3 percent; v: 0.07 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and then rolling and processing the alloy steel square billet into an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1200 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to be 1200 ℃, and keeping the temperature for 60 minutes to generate an oxide film with the average thickness of 20 mu m on the surface of the seamless steel pipe.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, the steel for corrosion resistance to sulfate-reducing bacteria comprises the following main chemical components in percentage by weight: c: 0.04 percent; si: 0.5 percent; mn: 0.5 percent; cr: 16 percent; cu: 1.5 percent; al: 3.5 percent; ce: 0.05 percent; mo: 0.6 percent; ti: 0.03 percent; the balance of Fe and inevitable impurities.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.04 percent; si: 0.5 percent; mn: 0.5 percent; cr: 16 percent; cu: 1.5 percent; al: 3.5 percent; ce: 0.05 percent; mo: 0.6 percent; ti: 0.03 percent; the balance of Fe and inevitable impurities; the method comprises the following steps of mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and processing into an alloy steel round billet through rolling;
b. heating the alloy steel round billet prepared in the step a to 1250 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to be 1200 ℃, and keeping the temperature for 90 minutes to generate an oxide film with the average thickness of 23 mu m on the surface of the seamless steel pipe.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, the steel for corrosion resistance to sulfate-reducing bacteria comprises the following main chemical components in percentage by weight: c: 0.03 percent; si: 0.2 percent; mn: 0.3 percent; cr: 22.3 percent; cu: 0.65 percent; al: 1.9 percent; ce: 0.01 percent; v: 0.06 percent; ti: 0.05 percent; the balance of Fe and inevitable impurities.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.03 percent; si: 0.2 percent; mn: 0.3 percent; cr: 22.3 percent; cu: 0.65 percent; al: 1.9 percent; ce: 0.01 percent; v: 0.06 percent; ti: 0.05 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and then rolling and processing the alloy steel square billet into an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1250 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to 1150 ℃ and the heat preservation time to 90 minutes, and generating an oxide film with the average thickness of 18 mu m on the surface of the seamless steel pipe.
Example five:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, the steel for corrosion resistance to sulfate-reducing bacteria comprises the following main chemical components in percentage by weight: c: 0.02 percent; si: 0.3 percent; mn: 0.4 percent; cr: 24 percent; cu: 1.3 percent; al: 1.5 percent; ce: 0.07 percent; mo: 0.2 percent; nb: 0.05 percent; the balance of Fe and inevitable impurities.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.02 percent; si: 0.3 percent; mn: 0.4 percent; cr: 24 percent; cu: 1.3 percent; al: 1.5 percent; ce: 0.07 percent; mo: 0.2 percent; nb: 0.05 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and rolling to prepare an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1270 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to 1250 ℃, and keeping the temperature for 60 minutes to generate an oxide film with the average thickness of 22 mu m on the surface of the seamless steel pipe. Table 1 shows the composition of the present invention in comparison to the prior art, as shown in table 1:
TABLE 1 comparison of the composition of similar products at home and abroad with the composition of the steel according to the invention (wt.%)
The steel for resisting the corrosion of the sulfate reducing bacteria prepared by the embodiment of the invention comprises the following chemical components in percentage by weight: c: less than or equal to 0.04 percent; si: 0.1-0.5%; mn: less than or equal to 0.5 percent; cr: 16-24%; cu: 0.15 to 1.5 percent; al: 1.5-3.5%; ce: 0.01 to 0.1 percent. The balance of Fe and inevitable impurities.
The oil well pipe for resisting sulfate reducing bacteria corrosion prepared by the embodiment of the invention comprises the following manufacturing method: smelting the chemical components, continuously casting the chemical components into a round billet, or casting the chemical components into a square billet and then rolling the square billet into a round billet; hot rolling into final product members such as seamless steel pipes; and then carrying out high-temperature annealing heat treatment, wherein the heating temperature is as follows: 1150-1250 ℃, heat preservation time: 60-120 minutes.
The product manufactured by the invention can effectively resist the corrosion of SRB in the external environment, has the yield strength of more than 380MPa, meets the requirement of J55 steel grade, and can well meet the problem that a pipe for water injection well oil extraction fails prematurely due to the corrosion of the SRB.
The manufacturing method of the SRB corrosion resistant steel of the embodiment of the invention is as follows:
molten steel having chemical compositions shown in table 2 was melted, continuously cast into a square billet, and then rolled into a round billet. Obtaining a final product component after hot rolling, producing a seamless steel pipe, and adopting a high-temperature annealing heat treatment process, wherein the heating temperature is as follows: 1150-1250 ℃, heat preservation time: and the average thickness of the oxide film generated on the surface is less than 60 mu m in 60-120 minutes.
For comparison with the alloy steel materials prepared in the above examples of the present invention, comparative test analyses were carried out using, in particular, alloy steel materials prepared in the following comparative examples:
comparative example one:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, an antibacterial stainless steel comprises the following main chemical components in percentage by weight: c: 0.02 percent; si: 0.2 percent; mn: 0.3 percent; cr: 20.1 percent; cu: 0.15 percent; al: 1.4 percent; ti: 0.05 percent; the balance of Fe and inevitable impurities. The comparative example antibacterial stainless steel does not contain Ce element.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.02 percent; si: 0.2 percent; mn: 0.3 percent; cr: 20.1 percent; cu: 0.15 percent; al: 1.4 percent; ti: 0.05 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and then rolling and processing the alloy steel square billet into an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1250 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to 1250 ℃, and keeping the temperature for 120 minutes to generate an oxide film with the average thickness of 25 mu m on the surface of the seamless steel pipe.
The antibacterial stainless steel of the comparative example does not contain Ce element, the Al element is 1.4 percent and is 1.5 percent lower than the lower limit of 1.5 to 3.5 percent of the Al element of the steel for resisting the corrosion of the sulfate reducing bacteria, and the chemical components (wt%) of the comparative example and the steel produced by the examples of the invention are compared with each other and are shown in Table 2.
Comparative example two:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, an antibacterial stainless steel comprises the following main chemical components in percentage by weight: c: 0.03 percent; si: 0.15 percent; mn: 0.5 percent; cr: 13 percent; cu: 0.9 percent; al: 2.1 percent; mo: 0.2 percent; ti: 0.03 percent; the balance of Fe and inevitable impurities. The comparative example antibacterial stainless steel does not contain Ce element.
In this embodiment, the method for preparing the steel for resisting corrosion by sulfate-reducing bacteria includes the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c: 0.03 percent; si: 0.15 percent; mn: 0.5 percent; cr: 13 percent; cu: 0.9 percent; al: 2.1 percent; mo: 0.2 percent; ti: 0.03 percent; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, preparing an alloy steel square billet through a continuous casting process after smelting, and then rolling and processing the alloy steel square billet into an alloy steel round billet;
b. heating the alloy steel round billet prepared in the step a to 1250 ℃, and then carrying out hot rolling to form a seamless steel pipe of a final product component;
c. and c, carrying out high-temperature annealing heat treatment on the seamless steel pipe prepared in the step b, controlling the heating temperature to 1250 ℃, and keeping the temperature for 120 minutes to generate an oxide film with the average thickness of 105 mu m on the surface of the seamless steel pipe.
The antibacterial stainless steel of the comparative example does not contain Ce element, the Cr element is 13 percent and is lower than the lower limit of 16-24 percent of the Cr element of the steel for resisting the corrosion of the sulfate reducing bacteria, and the chemical composition (wt%) of the comparative example is compared with that of the steel produced by each example of the invention, which is shown in Table 2.
Experimental test analysis:
the steel products produced according to the above examples and comparative examples of the present invention can be obtained as shown in table 2, and the chemical composition mass percentages of the steel products of different examples and comparative examples are specifically shown in table 2:
TABLE 2. examples and comparative examples chemistry (wt.%)
| Contrast item | C | Si | Mn | Cr | Cu | Al | Ce | Mo | V | Ti | Nb |
| Example one | 0.02 | 0.1 | 0.3 | 20.5 | 0.15 | 3.1 | 0.1 | 0.15 | 0.05 | ||
| Example two | 0.01 | 0.2 | 0.3 | 18.1 | 0.98 | 2.4 | 0.02 | 0.3 | 0.07 | ||
| EXAMPLE III | 0.04 | 0.5 | 0.5 | 16 | 1.5 | 3.5 | 0.05 | 0.6 | 0.03 | ||
| Example four | 0.03 | 0.2 | 0.3 | 22.3 | 0.65 | 1.9 | 0.01 | 0.06 | 0.05 | ||
| EXAMPLE five | 0.02 | 0.3 | 0.4 | 24 | 1.3 | 1.5 | 0.07 | 0.2 | 0.05 | ||
| Comparative example 1 | 0.02 | 0.2 | 0.3 | 20.1 | 0.15 | 1.4 | 0.05 | ||||
| Comparative example No. two | 0.03 | 0.15 | 0.5 | 13 | 0.9 | 2.1 | 0.2 | 0.03 |
The manufacturing method of the SRB corrosion resistant steel of the embodiment of the invention is as follows:
molten steel having the chemical composition shown in table 2 was subjected to melting, and then continuously cast into a round billet, or cast into a square billet and then rolled into a round billet. Obtaining a final product component after hot rolling, for example, producing a seamless steel pipe, and adopting a high-temperature annealing heat treatment process, wherein the heating temperature is as follows: 1150-1250 ℃, heat preservation time: and the average thickness of the oxide film generated on the surface is less than 60 mu m in 60-120 minutes.
Under different heat treatment process systems, the yield strength of the produced steel pipe is more than 380MPa, the requirement of J55 steel grade is met, and the heat treatment process and the mechanical property of the embodiment and each proportion are specifically shown in Table 3.
TABLE 3 Heat treatment process and mechanical properties of examples and comparative examples
Experiments and comparative analyses were carried out on the steels prepared in example one and comparative example one, and Φ 177.8 × 9.19 sleeves were respectively prepared by the preparation methods of example one and comparative example one, and the properties after heat treatment are shown in table 3. It can be seen from table 3 that the oil casings according to the present invention all meet the requirements of the J55 steel grade. In the first embodiment, the oxidation product on the surface of the steel pipe is fine and uniform, as shown in fig. 1, the oxidation film is embedded into the substrate in a wedge shape, as shown in fig. 2, the average thickness is 25 μm, and after a micro-indentation test, the oxidation film deforms along with the substrate without peeling or cracking, which indicates that the plasticity and the adhesion of the oxidation film are good, and the subsequent corrosion process of the SRB to the steel pipe can be effectively blocked; and the first comparative example does not contain rare earth Ce, and after the micro-indentation test, the oxide film is cracked, which shows that the plasticity of the oxide film is poor, the oxide film is easy to crack under the action of external force and cannot block SRB, and the corrosion resistance is naturally reduced. The comparative example No. two contained Cr too much, and the surface oxide film thickness exceeded 100 μm but was very likely to peel off, which was the main cause of reducing the effect on the SRB corrosion. In addition, the steel prepared in the first embodiment and the steel prepared in the first comparative embodiment are subjected to mechanical experiment comparative analysis, and under the condition of the external force of the box body, the magnesium oxide on the surface of the steel deforms as shown in fig. 3 and 4, so that the oxide film on the surface of the steel prepared in the first embodiment has higher strength and smaller deformation, and the visible steel has more excellent strength performance, is particularly suitable for being applied to service under more severe working conditions, is particularly suitable for being applied to fossil energy exploration, exploitation and conveying pipelines and other sulfate reducing bacteria corrosion-resistant process parts, and is particularly suitable for being applied to oil well pipes. In the above examples of the present invention, referring to tables 2 and 3, the overall properties of the steels prepared in examples two, three and five are apparently due to the properties of the steels prepared in the above comparative examples; particularly, the comprehensive properties of the steels prepared in the second embodiment and the third embodiment are more remarkable in strength advantage and yield strength and tensile strength light mechanical property on the basis of an oxide film with a certain thickness under the condition of ensuring that the toughness is comparable to the toughness of the steels prepared in the comparative examples, and the steels prepared in the second embodiment and the third embodiment have wider application fields.
Compared with the prior art, the steel for resisting the corrosion of the sulfate reducing bacteria, which is produced by the embodiment of the invention, is applied to the petroleum casing pipe, and has the following outstanding advantages and beneficial effects:
the oil well pipe made of the steel for the oil well pipe, which is obtained according to the component design and the process of the invention, has excellent mechanical property and triple protection effect on the aspect of resisting SRB corrosion:
1. blocking effect of oxide film: the rare earth Ce is added to obviously improve the toughness of the oxide film, so that a compact and strong-adhesion oxide film is generated on the surface of the steel;
2. poisoning effects of alloying elements on SRB in the event of surface oxide film cracking;
3. the electrode potential of the steel is improved, so that the SRB electrochemical corrosion resistance is improved.
The steel for resisting the corrosion of the sulfate reducing bacteria produced by the embodiment of the invention can well meet the requirement of the harsh environment of the oil extraction pipe of the water injection well. In addition, the preparation process of the steel for resisting the corrosion of the sulfate reducing bacteria, which is produced by the embodiment of the invention, mainly adopts low-cost alloy elements such as Cr, Cu, Al and the like, so that the cost of the steel pipe is moderate, and the steel pipe has great economic and social benefits.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention may be made in equivalent substitution ways, so long as the purpose of the present invention is met, and the technical principles and inventive concepts of the steel for corrosion resistance to sulfate-reducing bacteria, the application thereof and the preparation method thereof are not departed from the technical principles and inventive concepts of the present invention.
Claims (11)
1. The steel for resisting the corrosion of the sulfate reducing bacteria is characterized by comprising the following main chemical components in percentage by weight: c is less than or equal to 0.04 percent; si: 0.1-0.5%; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.65-1.5%; al: 1.5-3.1%; ce: 0.01-0.1%; the balance of Fe and inevitable impurities;
the steel for resisting the corrosion of the sulfate reducing bacteria is prepared by the following method, and comprises the following steps:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c is less than or equal to 0.04 percent; si: 0.1-0.5%; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.65-1.5%; al: 1.5-3.1%; ce: 0.01-0.1%; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, and then directly performing continuous casting to form an alloy steel primary blank, or firstly preparing an alloy steel ingot by a casting process, and then rolling to form an alloy steel primary blank;
b. heating the alloy steel primary blank prepared in the step a to 1250-1300 ℃, and then carrying out hot rolling to form a product component;
c. c, carrying out high-temperature annealing heat treatment on the product component prepared in the step b, controlling the heating temperature to 1150-1250 ℃, keeping the temperature for 60-120 minutes, and finally carrying out furnace cooling on the annealed product component to generate SRB corrosion resistant Cr on the surface of the material of the steel for resisting sulfate reducing bacteria corrosion2O3/Al2O3And a composite oxide film having an average thickness of 18 μm or more and less than 60 μm.
2. The sulfate-reducing bacteria corrosion-resistant steel according to claim 1, wherein: the chemical components are calculated according to weight percentage, wherein C: 0.01-0.04%; mn: 0.3 to 0.5 percent.
3. The sulfate-reducing bacteria corrosion-resistant steel according to claim 2, characterized in that: the chemical components are calculated according to weight percentage, wherein, Si: 0.2-0.5%; cu: 0.98-1.5%; ce: 0.02-0.07%.
4. The sulfate-reducing bacteria corrosion resistant steel according to claim 3, wherein: the chemical components are calculated according to weight percentage, wherein the weight ratio of Cr: 16-18.1%; al: 2.4-3.1%; ce: 0.02-0.05%.
5. The steel for sulfate-reducing bacteria corrosion resistance according to any one of claims 1 to 4, characterized in that: the chemical components of the alloy also comprise at least any two of Mo less than or equal to 0.6 wt%, V less than or equal to 0.15 wt%, Ti less than or equal to 0.05 wt% and Nb less than or equal to 0.05 wt%.
6. The sulfate-reducing bacteria corrosion resistant steel according to claim 5, wherein: the chemical components are calculated according to weight percentage, wherein Mo: 0.2-0.6%, V: 0.06-0.15%; ti: 0.03 to 0.05 percent.
7. The sulfate-reducing bacteria corrosion-resistant steel according to claim 6, characterized in that: the chemical components are calculated according to weight percentage, wherein Mo: 0.3 to 0.6 percent.
8. Use of a steel for corrosion resistance against sulfate-reducing bacteria according to claim 1, wherein: the steel is used as steel for oil well pipes of oil and gas wells.
9. A method of producing the sulfate-reducing bacteria corrosion resistant steel according to claim 1, comprising the steps of:
a. the steel for resisting the corrosion of the sulfate reducing bacteria comprises the following main chemical components in percentage by weight:
c is less than or equal to 0.04 percent; si: 0.1-0.5%; mn is less than or equal to 0.5 percent; cr: 16-24%; cu: 0.65-1.5%; al: 1.5-3.1%; ce: 0.01-0.1%; the balance of Fe and inevitable impurities; mixing the chemical component raw materials, smelting, and then directly performing continuous casting to form an alloy steel primary blank, or firstly preparing an alloy steel ingot by a casting process, and then rolling to form an alloy steel primary blank;
b. heating the alloy steel primary blank prepared in the step a to 1250-1300 ℃, and then carrying out hot rolling to form a product component;
c. and c, carrying out high-temperature annealing heat treatment on the product component prepared in the step b, controlling the heating temperature to 1150-1250 ℃, keeping the temperature for 60-120 minutes, and finally carrying out furnace cooling on the annealed product component, namely generating an oxide film on the surface of the material of the steel for resisting the corrosion of the sulfate reducing bacteria.
10. The method of producing a steel for corrosion resistant to sulfate-reducing bacteria according to claim 9, characterized in that: in the step b, the hot rolling temperature is controlled to be 1250-1270 ℃ when the hot rolling is carried out.
11. The method of producing a steel for corrosion resistant to sulfate-reducing bacteria according to claim 10, characterized in that: in the step c, when high-temperature annealing heat treatment is carried out, the heating temperature is controlled to 1250 ℃, and the heat preservation time is 60-90 minutes.
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