CN107400835A - Resistance to sulfate reducing bacteria corrosion steel, its application and preparation method thereof - Google Patents
Resistance to sulfate reducing bacteria corrosion steel, its application and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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Abstract
The invention discloses a kind of resistance to sulfate reducing bacteria corrosion steel, its application and preparation method thereof, its steel main chemical compositions percentage by weight is：C≤0.04%；Si：0.1~0.5%；Mn≤0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~3.5%；Ce：0.01~0.1%.Remaining is Fe and inevitable impurity.The resistance to sulfate reducing bacteria corrosion steel making method of the present invention includes：Smelted after raw material is mixed, cast and be configured to final products component；Subsequent high annealing heat treatment, heating-up temperature are 1150~1250 DEG C, and soaking time is 60~120 minutes.Present invention manufacture steel can be reasonably resistant to external environment condition SRB corrosion, and yield strength is more than 380 MPa, meets the requirement of J55 grade of steels, can meet well such as water injection well oil recovery pipe because SRB corrodes and premature failure.
Description
Technical field
The present invention relates to a kind of stainless steel and preparation method thereof, more particularly to a kind of resistance to bacterial corrosion steel and its preparation
Method, applied to fossil energy exploration, exploitation and conveyance conduit and other process components of resistance to sulfate reducing bacteria corrosion steel skill
Art field.
Background technology
High pour point oil reservoir is distributed more widely in the world, and oil in place is extremely abundant.The Liaohe River, Jilin, huge port, the Henan in China
There is the high pour point oil reservoir of suitable reserves Deng oil field, its common feature is that paraffin content is high, freezing point is high.Due to high pour point oil reservoir
There is its special property, note normal-temperature water exploitation can effectively improve oil reservoir ultimate recovery.Due to long-term a large amount of water fillings, so that
Cryosphere band is formed around water injection well, the condition such as its temperature and anoxic is especially suitable for the growth and breeding of bacterium.Again due to injecting water
Endlessly bring nutriment into so that sulfate reducing bacteria (Sulphate-Reducing Bacteria, SRB) etc. has
The amount reproduction of evil bacterium is possibly realized.
SRB descends oil well pipe caustically, it is destroyed by pitting corrosion.As certain oil-field flooding casing is gone into the well using 1
After month, corrosion failure occurs for steel pipe, and SRB contents are up to 5000-10000/ml after testing.The corrosion of sulfate reducing bacteria
Mainly due to the effect of hydrogenase, the mechanism of metal erosion is caused in two steps：The first step is bacterium by hydrogenase from metal
Surface releases atom state hydrogen, and helps hydrogen atom by sulfate reduction sulphidisation；Second step is cathodic depolarization effect.Cause
The problem of this SRB corrosion is substantially electrochemical corrosion.
The antibacterial steel produced both at home and abroad at present is mainly for strains such as Escherichia coli and staphylococcus aureus.Such as Chinese patent
CN200510013238.9 is related to a kind of austenite antimicrobial stainless steel, and its chemical component weight percentage (wt%) scope is as follows：
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≤0.02, P≤0.03, Si：0.1-1, remaining is Fe, referring to table 1；For another example Chinese patent
A kind of ferrite antibacterial stainless steel that CN02144568.0 is announced, its chemical composition are C≤0.2%, Si≤3%, Mn≤2%,
Cr：10-30%, Cu：0.4-2.2%, Zn≤1%, surplus is Fe and inevitable impurity, referring to table 1.This kind of antibacterial steel
Antibacterial Mechanism mainly relies on ε-Cu or Ag precipitated phases, with durable antibiotic performance, antibacterial range extensively and with good machinery
Performance and corrosion resistance.
Due to feature of the corrosion with electrochemical corrosion of SRB bacteriums, in order to improve the electrochemical corrosion performance of material, carry
The electrode potential of high steel is one of effective measures.Patent CN201210211075.5 starts with from this angle, using Cr：
8.5-25%； Cu：0.15-2.5%；Al：0.5-3.5% chemical composition, preferable effect is achieved, referring to table 1.However,
Because sulfate reducing bacteria is not easy to be found in the fluid of flowing, but being attached on pipeline in groups or into bacterium colony.Therefore
Once in the presence of it is difficult to which it is thoroughly removed by using bactericide.Have not yet to see about being highly resistant to SRB corrosion
The report of steel.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Resistance to sulfate reducing bacteria corrosion steel, its application and preparation method thereof.It is secondary in oil as oil field development enters the middle and later periods
In oil-extracting and water-injecting system, asked to solve the corrosion of the oil well pipe caused by sulfate reducing bacteria (SRB) amount reproduction
Topic, because the premise of SRB microbiologic(al) corrosions is bacterium in the absorption of metal surface and forms biomembrane, the present invention passes through production
During flexible sull is formed in metal surface, with block SRB metal surface occur absorption and its produce electrification
Process, so as to effectively solve SRB etching problem；On the other hand, it is contemplated that oxide-film breakage can cause SRB to material
Corrosion, take antibacterial alloying element to carry out alloy design, while improve the resistance to electrochemical corrosion energy of material itself.The present invention
Purpose is to provide a kind of steel and oil pipe production method for being effective against SRB corrosion, to meet that water injection well SRB corrodes
The corrosion resistant performance requirement proposed to material.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：C≤0.04%；Si：
0.1~0.5%；Mn≤0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~3.5%；Ce：0.01~
0.1%；Remaining is Fe and inevitable impurity.
Calculate in percentage by weight, in preferred resistance to sulfate reducing bacteria corrosion steel chemical composition, C：0.01~
0.04%； Mn：0.3~0.5%.
Calculate in percentage by weight, in further preferred resistance to sulfate reducing bacteria corrosion steel chemical composition, Si：
0.2~0.5%；Cu：0.98~1.5%；Ce：0.02~0.07%.
Calculate in percentage by weight, in still more preferably resistance to sulfate reducing bacteria corrosion steel chemical composition, Cr：
16~18.1%；Al：2.4~3.5%；Ce：0.02~0.05%.
As the further preferred technical scheme of such scheme, its chemical composition is calculated in percentage by weight also includes Mo
At least any two kinds of compositions in≤0.6wt%, V≤0.15wt%, Ti≤0.05wt% and Nb≤0.05wt%.According to weight
Percentage is measured to calculate, in further preferred resistance to sulfate reducing bacteria corrosion steel chemical composition, Mo：0.2~0.6%, V：
0.06~0.15%； Ti：0.03~0.05%.Calculate in percentage by weight, in still more preferably resistance to sulfate reducing bacteria
Corrosion is with tempering chemical composition, Mo：0.3~0.6%.
A kind of application of the resistance to sulfate reducing bacteria corrosion steel of the present invention, makes as petroleum and natural gas well steel for oil well pipes
With.
A kind of preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present invention, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C≤0.04%；Si：0.1~0.5%；Mn≤0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~
3.5%； Ce：0.01~0.1%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, carry out
Smelt, then direct continuous casting is configured to steel alloy just base, or the method combined using founding with later stage processing, first leads to
Cross founding and be made steel alloy ingot casting, then base at the beginning of being processed into steel alloy by rolling；
B. after base at the beginning of the steel alloy that will be prepared in the step a is heated to 1200~1300 DEG C, hot rolling is carried out, is configured to
Product members；When carrying out hot rolling, it is 1200~1270 DEG C preferably to control hot-rolled temperature；
C. high annealing heat treatment is carried out to the product members prepared in the step b, it is 1150 to control heating-up temperature
~1250 DEG C, soaking time is 60~120 minutes.Carry out high annealing heat treatment when, preferably control heating-up temperature be 1200~
1250 DEG C, preferably soaking time is 60~90 minutes, furnace cooling, i.e., resistance to sulfuric acid finally are carried out to the product members after annealing
The material surface generation oxide-film of salt reducing bacteria corrosion steel.The present invention takes high annealing thermal treatment production process system to production
Product component carries out final heat treatment, after furnace cooling, is less than 60 in the thickness average value of steel surface generation prepared by the present invention
μm fine and close oxide-film.
It is the action principle of each chemical composition of the resistance to sulfate reducing bacteria corrosion steel of the present invention below and its illustrates：
C：The intensity of steel can be effectively improved, but too high levels make it that oxide-film is loose, comes off, and reduction shows to aoxidize film quality
Amount, by weight percentage, preferably using phosphorus content≤0.04%.
Si：Ferrite is solid-solution in improve the yield strength of steel, but plasticity and toughness can be lost simultaneously, can be effectively improved
The passivation ability of steel, so as to improve the corrosion resistance of steel, by weight percentage, silicone content is preferably used as 0.1~0.5%.
Mn：The main ferrite that is dissolved in plays invigoration effect, but segregation is serious when content is too high, SRB corrosive natures is reduced, by weight
Percentage is measured, preferably uses Mn contents as≤0.5%.
Cr：Effectively improve the anti-SRB corrosive natures of steel.Cr significantly improves the electrode potential of steel, and its mol ratio follows n/8 rule
Restrain, Cr is formed under high temperature2O3Film, it can effectively separate SRB attachment, while Cr has toxicity to SRB, is unfavorable for SRB life
It is long.When Cr contents are less than 16%, the coating mass of formation is poor.But the increase of Cr too high levels cost, by weight percentage,
Preferably use content 16~24%.
Cu：Be advantageous to improve the intensity of steel, while effectively improve the anti-SRB corrosive natures of steel, but can make during too high levels
Obtain steel and the crisp phenomenons of Cu occur, by weight percentage, preferably using content 0.15~1.5%.
Al：Deoxidation nitrogen killer, the passivation ability of steel can be effectively improved, improve the corrosion resistance of steel, improve oxide-film
Quality, effectively improves the anti-SRB corrosive natures of steel, steel fragility is increased during too high levels, by weight percentage, preferably adopted
With content 1.5~3.5%.
Ce：The diffusion process of ion in oxide-film is effectively hindered, has and significantly improves Cr2O3/Al2O3Complex oxide film is tough
The effect of property, single content are costly when high, so by weight percentage, preferably using content 0.01~0.1%.
Mo：Steel belt roof bolt stability is improved, is advantageous to improve the intensity and corrosion resistance of steel, there is the anti-corrosion of satisfaction
Property.It is costly when content is high, by weight percentage, preferably using content≤0.6%.
V：Strong carbonitride-forming elements, for adjusting the intensity of steel.If content is too high, cost is too high, by weight percentage
Than preferably using content≤0.15%.
Ti：Strong carbonitride-forming elements, for adjusting the intensity of steel；If content is too high, thick TiN is easily formed.Press
Percentage by weight, preferably using content≤0.05%.
Nb：Strong carbonitride-forming elements, it can effectively adjust the intensity of steel.If content is too high, cost is too high, by weight
Percentage, preferably using content≤0.05%.
The mechanism of alloy design of the present invention is as follows：
1) addition Cr, Al generates the moderate Cr of thickness in process of production2O3/Al2O3Complex oxide film, addition Ce improve
The toughness of oxide-film so that the oxide-film of steel surface generation is fine and close, adhesiveness is by force so as to separating SRB corrosion；
2) electrode potential that Cr, Al also improve steel simultaneously is added, improves anti-SRB electrochemical corrosion performances；
3) elements such as Cr, Cu are added, suppress SRB breeding and growth using its toxicity to SRB；
4) alloying elements such as Mo, Nb, V, Ti are added so that steel grade reaches appropriate strength level.
The steel of the present invention and the manufacture method of oil pipe are as follows：Molten steel according to the chemical composition of the present invention passes through melting
Afterwards, round billet is casting continuously to form, or round billet is rolled into after being cast into square billet.Hot rolling after being heated to 1250 ± 50 DEG C, the steel of acquisition or seamless
Steel pipe takes high annealing thermal treatment production process system, heating-up temperature：1150~1250 DEG C, soaking time：60~120 points
Clock, furnace cooling, the oxide thickness average value of Surface Creation are less than 60 μm.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention takes the thermal treatment production process system of high annealing, on the one hand, the oxide-film formed at high temperature
Thickness is suitable, and caused stress can effectively eliminate in tempering in cooling procedure；On the other hand, can be eliminated under high temperature
It is segregated tissue so that homogenization of composition, precipitation diffuses in follow-up cooling, the second uniform, tiny phase reaches the matrix of reinforcing
Effect；This heat treating regime can ensure to ensure to obtain while excellent mechanical property is obtained have good anti-SRB
The oxide-film of performance；
2. anti-SRB steel and manufactured oil well pipe that composition design and its technique that the present invention uses obtain have excellent
Mechanical property, the SRB corrosion of external environment condition can be reasonably resistant to, water injection well oil recovery pipe severe rugged environment can be met well
Requirement.
Brief description of the drawings
Fig. 1 is the microcosmic of the oxide-film that resistance to sulfate reducing bacteria corrosion steel surface prepared by the embodiment of the present invention one is formed
Photo.
Fig. 2 is that resistance to sulfate reducing bacteria corrosion oxide film on steel surface Cross Section Morphology prepared by the embodiment of the present invention one is microcosmic
Photo.
After the oxide-film deformation that Fig. 3 is formed for resistance to sulfate reducing bacteria corrosion steel surface prepared by the embodiment of the present invention one
Photo.
After the oxide-film deformation that Fig. 4 is formed for resistance to sulfate reducing bacteria corrosion steel surface prepared by comparative example one of the present invention
Photo.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, a kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：
C：0.02%；Si：0.1%；Mn：0.3%；Cr：20.5%；Cu：0.15%；Al：3.1%；Ce：0.1%；V：0.15%；
Nb：0.05%；Remaining is Fe and inevitable impurity.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.02%；Si：0.1%；Mn：0.3%；Cr：20.5%；Cu：0.15%；Al：3.1%；Ce：0.1%；V：
0.15%； Nb：0.05%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted,
After melting, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1300 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1250 to control heating-up temperature
DEG C, soaking time is 120 minutes, is 25 μm of oxide-film in seamless steel pipe Surface Creation average thickness, referring to Fig. 1 and Fig. 2.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：
C：0.01%；Si：0.2%；Mn：0.3%；Cr：18.1%；Cu：0.98%；Al：2.4%；Ce：0.02%；Mo：0.3%；
V：0.07%；Remaining is Fe and inevitable impurity.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.01%；Si：0.2%；Mn：0.3%；Cr：18.1%；Cu：0.98%；Al：2.4%；Ce：0.02%；Mo：
0.3%；V：0.07%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted, passed through
After crossing melting, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1200 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1200 to control heating-up temperature
DEG C, soaking time is 60 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 20 μm.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：
C：0.04%；Si：0.5%；Mn：0.5%；Cr：16%；Cu：1.5%；Al：3.5%；Ce：0.05%；Mo：0.6%；Ti：
0.03%；Remaining is Fe and inevitable impurity.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.04%；Si：0.5%；Mn：0.5%；Cr：16%；Cu：1.5%；Al：3.5%；Ce：0.05%；Mo：
0.6%； Ti：0.03%；Remaining is Fe and inevitable impurity；After it mixes above-mentioned chemical composition raw material, smelting is carried out
Refining, after melting, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1250 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1200 to control heating-up temperature
DEG C, soaking time is 90 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 23 μm.
Example IV：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：
C：0.03%；Si：0.2%；Mn：0.3%；Cr：22.3%；Cu：0.65%；Al：1.9%；Ce：0.01%；V：0.06%；
Ti：0.05%；Remaining is Fe and inevitable impurity.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.03%；Si：0.2%；Mn：0.3%；Cr：22.3%；Cu：0.65%；Al：1.9%；Ce：0.01%；V：
0.06%；Ti：0.05%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted,
After melting, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1250 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1150 to control heating-up temperature
DEG C, soaking time is 90 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 18 μm.
Embodiment five：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of resistance to sulfate reducing bacteria corrosion steel, the percentage by weight of its main chemical compositions are：
C：0.02%；Si：0.3%；Mn：0.4%；Cr：24%；Cu：1.3%；Al：1.5%；Ce：0.07%；Mo：0.2%；Nb：
0.05%；Remaining is Fe and inevitable impurity.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.02%；Si：0.3%；Mn：0.4%；Cr：24%；Cu：1.3%；Al：1.5%；Ce：0.07%；Mo：
0.2%； Nb：0.05%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted,
After melting, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1270 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1250 to control heating-up temperature
DEG C, soaking time is 60 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 22 μm.Table 1 shows the present invention
Contrasted with the composition of prior art, it is specific as shown in table 1：
The composition contrast (wt.%) of the composition of 1. domestic and international similar products of table and steel of the present invention
Resistance to sulfate reducing bacteria corrosion steel prepared by the above embodiment of the present invention, the percentage by weight of its chemical composition
For：C：≤ 0.04%；Si：0.1~0.5%；Mn：≤ 0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~
3.5%；Ce：0.01~0.1%.Remaining is Fe and inevitable impurity.
Resistance to sulfate reducing bacteria corrosion oil well pipe prepared by the above embodiment of the present invention, its manufacture method include：Will be upper
Chemical composition smelting is stated, is casting continuously to form round billet, or round billet is rolled into after being cast into square billet；Final products component is rolled into, it is such as seamless
Steel pipe；Subsequent high annealing heat treatment, heating-up temperature：1150~1250 DEG C, soaking time：60~120 minutes.
Product produced by the present invention can be reasonably resistant to external environment condition SRB corrosion, and yield strength is more than 380MPa, full
The requirement of sufficient J55 grade of steels, it can meet such as water injection well oil recovery pipe because of SRB corrosion and the problem of premature failure well.
The manufacture method of the resistance to SRB corrosion steel of the above embodiment of the present invention is as follows：
Molten steel with the chemical composition shown in table 2 is rolled into round billet after melting after being casting continuously to form square billet.Obtained after hot rolling
Final products component is obtained, seamless steel pipe is produced, using high annealing Technology for Heating Processing, heating-up temperature：1150~1250 DEG C, protect
The warm time：60~120 minutes, the oxide thickness average value of Surface Creation was less than 60 μm.
In order to be contrasted with alloy steel material prepared by the above embodiment of the present invention, especially prepared using following comparative example
Alloy steel material carry out comparison test analysis：
Comparative example one：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of anti-bacteria stainless steel, the percentage by weight of its main chemical compositions are：C：0.02%；Si：
0.2%； Mn：0.3%；Cr：20.1%；Cu：0.15%；Al：1.4%；Ti：0.05%；Remaining be Fe and inevitably it is miscellaneous
Matter.Ce elements are not contained in this comparative example anti-bacteria stainless steel.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.02%；Si：0.2%；Mn：0.3%；Cr：20.1%；Cu：0.15%；Al：1.4%；Ti：0.05%；Its
Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted, after melting, pass through continuous casting
Alloy billet is made in technique, then is processed into alloyed steel round billet by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1250 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1250 to control heating-up temperature
DEG C, soaking time is 120 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 25 μm.
Ce elements are not contained in this comparative example anti-bacteria stainless steel, and Al elements are 1.4%, less than the resistance to sulfate of the present invention also
The Al elements of opportunistic pathogen corrosion steel are 1.5~3.5% lower limit 1.5%, this comparative example and the steel of various embodiments of the present invention production
The chemical composition (wt%) of material is contrasted referring to table 2.
Comparative example two：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of anti-bacteria stainless steel, the percentage by weight of its main chemical compositions are：C：0.03%；Si：
0.15%； Mn：0.5%；Cr：13%；Cu：0.9%；Al：2.1%；Mo：0.2%；Ti：0.03%；Remaining is Fe and can not
The impurity avoided.Ce elements are not contained in this comparative example anti-bacteria stainless steel.
In the present embodiment, the preparation method of the resistance to sulfate reducing bacteria corrosion steel of the present embodiment, comprises the following steps：
A. raw material is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion to match somebody with somebody
Than：
C：0.03%；Si：0.15%；Mn：0.5%；Cr：13%；Cu：0.9%；Al：2.1%；Mo：0.2%；Ti：
0.03%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelted, by melting
Afterwards, alloy billet is made by continuous casting process, then alloyed steel round billet is processed into by rolling；
B. after the alloyed steel round billet prepared in the step a being heated into 1250 DEG C, hot rolling is carried out, is configured to finally produce
Product component seamless steel pipe；
C. high annealing heat treatment is carried out to the seamless steel pipe prepared in the step b, it is 1250 to control heating-up temperature
DEG C, soaking time is 120 minutes, in the oxide-film that seamless steel pipe Surface Creation average thickness is 105 μm.
Ce elements are not contained in this comparative example anti-bacteria stainless steel, and Cr elements are 13%, less than the resistance to sulfate of the present invention also
The Cr elements of opportunistic pathogen corrosion steel are 16~24% lower limit 16%, this comparative example and the steel of various embodiments of the present invention production
Chemical composition (wt%) contrast referring to table 2.
Experimental test and analysis：
The steel produced according to the above embodiment of the present invention and comparative example can be used as shown in table 2, to different embodiments
It is specific as shown in table 2 with the chemical analysis mass percent of comparative example steel：
The embodiment of table 2. and comparative example chemical composition (wt.%)
| Contrast project | C | Si | Mn | Cr | Cu | Al | Ce | Mo | V | Ti | Nb |
| Embodiment one | 0.02 | 0.1 | 0.3 | 20.5 | 0.15 | 3.1 | 0.1 | 0.15 | 0.05 | ||
| Embodiment two | 0.01 | 0.2 | 0.3 | 18.1 | 0.98 | 2.4 | 0.02 | 0.3 | 0.07 | ||
| Embodiment three | 0.04 | 0.5 | 0.5 | 16 | 1.5 | 3.5 | 0.05 | 0.6 | 0.03 | ||
| Example IV | 0.03 | 0.2 | 0.3 | 22.3 | 0.65 | 1.9 | 0.01 | 0.06 | 0.05 | ||
| Embodiment five | 0.02 | 0.3 | 0.4 | 24 | 1.3 | 1.5 | 0.07 | 0.2 | 0.05 | ||
| Comparative example one | 0.02 | 0.2 | 0.3 | 20.1 | 0.15 | 1.4 | 0.05 | ||||
| Comparative example two | 0.03 | 0.15 | 0.5 | 13 | 0.9 | 2.1 | 0.2 | 0.03 |
The manufacture method of the resistance to SRB corrosion steel of the above embodiment of the present invention is as follows：
Molten steel with the chemical composition shown in table 2 is casting continuously to form round billet after melting, or is rolled into after being cast into square billet
Round billet.Final products component is obtained after hot rolling, seamless steel pipe is such as produced, using high annealing Technology for Heating Processing, heating-up temperature：
1150~1250 DEG C, soaking time：60~120 minutes, the oxide thickness average value of Surface Creation was less than 60 μm.
Under different system of heat treatment process, the yield strength of the steel pipe of production is both greater than 380MPa, meets J55 grade of steels
Requirement, the Technology for Heating Processing and mechanical property of the above embodiment of the present invention and above-mentioned each comparative example be specifically as shown in table 3.
The embodiment of table 3. and comparative example Technology for Heating Processing and mechanical property
Experimental contrast analysis is carried out with steel prepared by embodiment one and comparative example one, passes through embodiment one and comparative example one
Preparation method prepares the sleeve pipes of Ф 177.8 × 9.19 respectively, and after heat treatment performance is shown in Table 3.It can see by table 3, according to this
The petroleum casing pipe of invention can meet the requirement of J55 grade of steels.The oxidation product fine uniform of the steel tube surface of embodiment one, is shown in figure
1, oxide-film is shown in Fig. 2 in chock shape insertion matrix, and thickness average value is 25 μm, after carrying out micro indentation test, oxide-film with
Deformed together with matrix, do not peel off or ftracture, illustrate oxide-film plasticity and good adhesion, SRB pairs can be effectively blocked
The subsequent corrosion process of steel pipe；And comparative example one is free of Rare-Earth Ce, after carrying out micro indentation test, oxide-film cracking, explanation
Oxide-film plasticity is poor, is easy to ftracture and can not play a part of blocking SRB under external force, corrosion resistance is natural
Decline.The Cr contents of comparative example two are too low, although surface oxidation film thickness more than 100 μm, is very easy to peel off, this is drop
It is low to SRB corrosion effect the main reason for.The steel prepared in addition with embodiment one and comparative example one carry out Experiments of Machanics pair
Than analysis, under the outer force conditions of casing, the situation of the magnesia deformation of steel surface is as shown in Figure 3 and Figure 4, it is seen that
The oxidation film strength of steel surface prepared by embodiment one is higher, and deformation is smaller, it is seen that and the intensity performance of steel is more excellent,
It is particularly suitable for application to be on active service under harsher operating mode, particularly suitable for fossil energy exploration, exploitation and conveying
Pipeline and other process components of resistance to sulfate reducing bacteria corrosion, are particularly suitable for application to oil well pipe.In the above embodiment of the present invention
In, referring to table 2 and table 3, the combination property of steel prepared by embodiment two, example three and embodiment five is substantially due to above-mentioned contrast
The performance of steel prepared by example；Especially the combination property of steel prepared by embodiment two and example three ensure that toughness with
Under the conditions of the tough sex expressions of steel prepared by above-mentioned comparative example is equal, and in the base with certain thickness oxide-film
On plinth, more outstanding behaviours is that strength advantage is obvious, and yield strength and the slight mechanical characteristic of stretch-proof are had outstanding performance, and ensure that
Steel prepared by embodiment two and example three, which have, is more widely applied field.
Compared with prior art, the resistance to sulfate reducing bacteria corrosion produced using the above embodiment of the present invention is applied to steel
Petroleum casing pipe, there is the advantages of following prominent and beneficial effect：
Oil well pipe made of the steel for oil well pipes that composition design and its technique according to the present invention obtain has excellent power
Performance is learned, there are triple protection effects in terms of SRB corrosion is resisted：
1. the cut-off effect of oxide-film：Addition Rare-Earth Ce is obviously improved the toughness of oxide-film so that steel surface generation is fine and close
, the oxide-film that adhesiveness is strong；
2. in the case where surface film oxide ruptures, poisoning effect of the alloying element to SRB；
3. the electrode potential of steel is improved so as to improve anti-SRB electrochemical corrosion performances.
The resistance to sulfate reducing bacteria corrosion steel of the above embodiment of the present invention production can meet that water injection well recovers the oil well and use
The requirement of pipe severe rugged environment.Further, since the preparation of the resistance to sulfate reducing bacteria corrosion steel of the above embodiment of the present invention production
Technique mainly using alloying elements such as Cr, Cu, Al of low cost, steel pipe moderate cost, has great economy and society's effect
Benefit.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with
A variety of changes, all Spirit Essences and principle according to technical solution of the present invention are made according to the purpose of the innovation and creation of the present invention
Under change, modification, replacement, combination or the simplification made, equivalent substitute mode is should be, as long as meeting the invention mesh of the present invention
, technical principle and invention without departing from the resistance to sulfate reducing bacteria corrosion steel of the present invention, its application and preparation method thereof
Design, belongs to protection scope of the present invention.
Claims (11)
1. a kind of resistance to sulfate reducing bacteria corrosion steel, it is characterised in that the percentage by weight of its main chemical compositions is：C≤
0.04%；Si：0.1~0.5%；Mn≤0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~3.5%；Ce：
0.01~0.1%；Remaining is Fe and inevitable impurity.
2. resistance to sulfate reducing bacteria corrosion steel according to claim 1, it is characterised in that：Its chemical composition is according to weight hundred
Divide than calculating, wherein C：0.01~0.04%；Mn：0.3~0.5%.
3. resistance to sulfate reducing bacteria corrosion steel according to claim 2, it is characterised in that：Its chemical composition is according to weight hundred
Divide than calculating, wherein Si：0.2~0.5%；Cu：0.98~1.5%；Ce：0.02~0.07%.
4. resistance to sulfate reducing bacteria corrosion steel according to claim 3, it is characterised in that：Its chemical composition is according to weight hundred
Divide than calculating, wherein Cr：16~18.1%；Al：2.4~3.5%；Ce：0.02~0.05%.
5. the resistance to sulfate reducing bacteria corrosion steel according to any one in Claims 1 to 4, it is characterised in that：Its chemistry
Composition calculate in percentage by weight also include Mo≤0.6wt%, V≤0.15wt%, Ti≤0.05wt% and Nb≤
At least any two kinds of compositions in 0.05wt%.
6. resistance to sulfate reducing bacteria corrosion steel according to claim 5, it is characterised in that：Its chemical composition is according to weight hundred
Divide than calculating, wherein Mo：0.2~0.6%, V：0.06~0.15%；Ti：0.03~0.05%.
7. resistance to sulfate reducing bacteria corrosion steel according to claim 6, it is characterised in that：Its chemical composition is according to weight hundred
Divide than calculating, wherein Mo：0.3~0.6%.
A kind of 8. application of resistance to sulfate reducing bacteria corrosion steel described in claim 1, it is characterised in that：As petroleum gas
Well steel for oil well pipes uses.
9. a kind of preparation method of resistance to sulfate reducing bacteria corrosion steel, it is characterised in that comprise the following steps：
A. raw material proportioning is carried out with the percentage by weight of the material main chemical compositions of steel according to resistance to sulfate reducing bacteria corrosion：
C≤0.04%；Si：0.1~0.5%；Mn≤0.5%；Cr：16~24%；Cu：0.15~1.5%；Al：1.5~
3.5%；Ce：0.01~0.1%；Remaining is Fe and inevitable impurity；After above-mentioned chemical composition raw material is mixed, smelting is carried out
Refining, then direct continuous casting is configured to steel alloy just base, or first passes through founding and steel alloy ingot casting is made, then is added by rolling
Base at the beginning of work into steel alloy；
B. after base at the beginning of the steel alloy that will be prepared in the step a is heated to 1200~1300 DEG C, hot rolling is carried out, is configured to product
Component；
C. high annealing heat treatment is carried out to the product members that are prepared in the step b, control heating-up temperature be 1150~
1250 DEG C, soaking time is 60~120 minutes, finally carries out furnace cooling to the product members after annealing, i.e., resistance to sulfate is also
The material surface generation oxide-film of opportunistic pathogen corrosion steel.
10. the preparation method of resistance to sulfate reducing bacteria corrosion steel according to claim 9, it is characterised in that：In the step
In rapid b, when carrying out hot rolling, it is 1200~1270 DEG C to control hot-rolled temperature.
11. the preparation method of resistance to sulfate reducing bacteria corrosion steel according to claim 9, it is characterised in that：In the step
In rapid c, when carrying out high annealing heat treatment, it is 1200~1250 DEG C to control heating-up temperature, and soaking time is 60~90 minutes.
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