CN1401809A - Carbon dioxide corrosion-resistant low alloy steel and oil casing - Google Patents

Carbon dioxide corrosion-resistant low alloy steel and oil casing Download PDF

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Publication number
CN1401809A
CN1401809A CN 01126575 CN01126575A CN1401809A CN 1401809 A CN1401809 A CN 1401809A CN 01126575 CN01126575 CN 01126575 CN 01126575 A CN01126575 A CN 01126575A CN 1401809 A CN1401809 A CN 1401809A
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Prior art keywords
steel
corrosion
carbon dioxide
alloy steel
low alloy
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CN 01126575
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CN1151305C (en
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张忠铧
郭金宝
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Abstract

A low-alloy steel resisting CO2 corrosion contains C (0.01-0.30%), Si (0.1-1.0%), Mn (0.1-2%), Cr (0.5-5.0%), Mo (0.01-1.0%), Cu (0.05-2 %), Ni (0.05-1%), Al (0.005-0.1%), optional rare-earth elements (0.005-0.25%), optional W (0.01-1%) and Fe (the rest). It can be used to manufacture the oil casing for oil or gas well with high resistance to CO2 corrosion and low cost.

Description

The low alloy steel of carbon dioxide corrosion-resistant and tubing and casing
Technical field
The present invention relates to a kind of low alloy steel and tubing and casing of carbon dioxide corrosion-resistant, particularly low alloy steel and the oil gas well tubing and casing that under combination of acidic corrosion working conditions such as moistening carbonic acid gas, chlorion, hydrogen sulfide, can use.
Background technology
The serious CO of present most of oil field ubiquity 2Etching problem.And it is annual because of CO 2The accident that corrosion is produced brings financial loss up to more than hundred million yuan to the oil field.From the anticorrosion angle of material, at high CO 2In the strong corrosive environment that high temperature, high pressure and fluid scouring form in content, chlorion, the output water yield, iron ion content, low pH value and the well, guarantee oilfield safety, produce efficiently that the most effective way is to use the above high chromium rust free steel tubing of expensive 13Cr.But because the most oil fields of China belong to the lean ore low permeability oil field, the production life of well of oil well uses expensive high chromium-stainless steel oil pipe mostly below 10 years, and the oil field can't be accepted, and economy is relatively poor.In addition, still there is comparatively serious local corrosion in high Cr stainless steel in the environment of this high chloride ion.Therefore most of oil fields have to be used general straight carbon steel tubing at present, thereby have caused a lot of serious CO in oil field 2The corrosion accident.Therefore, research and develop anti-CO 2Corrosive nature is better, moderate " economical " low-alloy tubing and casing of steel pipe cost has great economic and social benefit.
Find relevant anti-CO by retrieval 2Corrosion with in, nearly ten kinds of the patents of invention of low alloy steel, but these patents related all be relevant anti-CO basically 2The line of pipes Low Alloy Steel Plate and the manufacture method thereof of corrosion usefulness.Because the working conditions of pipe line steel and manufacture method and tubing and casing have than big-difference, CO in the transfer lime especially 2Dividing potential drop, temperature, flow velocity, strained condition etc. with the downhole oil sleeve pipe very big difference is arranged, it is to the corrodibility of the material also tubing and casing under the oil well.Therefore, can't be used to make tubing and casing.
Be used to make tubing and casing in the world and belong to the low alloy steel category, find that related to the present invention being used to make the patent of oil annular tube steel alloy and have two by retrieval, its patent No. is respectively EP 995809 and WO99/41422.Wherein the chemical ingredients of patent EP 995809 steel is: 0.10～0.30%C, 0.10～1.0%Si, 0.10～3.0%Mn, 2.0～9.0%Cr, 0.01～0.10%Al or 0.05～0.5%Cu, P≤0.03%, S≤0.01%, all the other are that Fe and inevitable impurity are formed.The contriver is mainly by adding Cr and the proper C u or the Al of more content, to improve the anti-CO of material 2With the sea-water corrosion performance, especially overcome the local corrosion phenomenon under the particular medium condition.But this patent interalloy amount of element is the add-on higher (surpassing 4% weight percent) of Cr especially, high alloy category in belonging to, the corresponding raising of the cost of steel pipe.In addition, this patent makes the martensitic stucture that is organized as of the finished product by special manufacture method.And the chemical ingredients of patent WO99/41422 steel is :≤0.3%C ,≤1.0%Si, 0.20～2.0%Mn, 2.1～5.0%Cr ,≤0.10%Al ,≤0.015%N, add a small amount of Cu in case of necessity, Ni, Mo, Ti, Nb, B, all the other are that Fe and inevitable impurity are formed, organizing of its finished product also is martensitic stucture.
The applicant once applied for a relevant anti-CO in 2000 2, Cl -The patent of corrosion oil annular tube steel is is also accepted through Patent Office, and application number is 00125882.6.C content belongs to the ultra low-carbon steel category below 0.10% in this patent.
Summary of the invention
In view of existing N80, oil bushing steels such as C90, P110 in that to contain under the combination of acidic corrosion working conditions such as carbonic acid gas, chlorion, hydrogen sulfide solidity to corrosion very poor, often bring with CO to the oil field 2Be main corrosion accident, and the existing defective of above-mentioned patent, the object of the present invention is to provide a kind of anti-CO 2Corrodibility, moderate " economical " low alloy steel and the tubing and casing of cost.
The low alloy steel of carbon dioxide corrosion-resistant of the present invention contains
C：?0.01～0.30％：?Si：0.10～1.0％
Mn：0.10～2.0％：??Cr：0.50～5.0％
Mo：0.01～1.0％：??Cu：0.05～2.0％
Ni：0.05～1.0％：??Al：0.005～0.1％；
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
The low alloy steel of carbon dioxide corrosion-resistant of the present invention contains
C：?0.01～0.30％：?Si：0.10～1.0％
Mn：0?10～2.0％：??Cr：0.50～5
Mo：0.01～1.0％：??Cu：0.05～2.0％
Ni：0.05～1.0％：??Al：0.005～0.1％；
Also contain rare earth 0.005～0.25%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
The low alloy steel of carbon dioxide corrosion-resistant contains:
C：?0.01～0.30％：?Si：0.10～1.0％
Mn：0.10～2.0％：??Cr：0.50～5.0％
Mo：0.01～1.0％：??Cu：0.05～2.0％
Ni：0.05～1.0％：??Al；0.005～0.1％；
Also contain W:0.01～1.0%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
The low alloy steel and the tubing and casing of carbon dioxide corrosion-resistant of the present invention contain
C：0.01～0.30％：??Si：0.10～1.0％
Mn：0.10～2.0％：??Cr：0.50～5.0％
Mo：0.01～1.0％：??Cu：0.05～2.0％
Ni：0.05～1.0％：??Al；0.005～0.1％；
Also contain rare earth 0.005～0.25%;
Also further contain W:0.01～1.0%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
The low alloy steel of carbon dioxide corrosion-resistant of the present invention can be used for making oil gas well tubing and casing
Steel alloy of the present invention is after modified or normalizing treatment, and its mechanical property has reached the requirement of API80,105 and 110 grade of steels.
Steel alloy of the present invention can be suitable for the oil gas well low-alloy steel for oil casing pipe under the combination of acidic corrosion working conditions such as carbonic acid gas, chlorion, hydrogen sulfide.
Steel alloy of the present invention selects the reason of chemical ingredients scope as follows:
C guarantees steel pipe room temperature strength and the necessary composition of hardening capacity, but when requiring to improve anti-CO 2And Cl -During corrosive nature, should limit carbon content.Carbon content is lower than 0.01% hardening capacity and insufficient strength, is higher than 0.30% back toughness and degenerates the corrodibility variation.
The compound adding of Mo and W has improved the particularly anti-local corrosion of high temperature of solidity to corrosion on the one hand, has improved the intensity and the hardening capacity of material in addition.Be lower than 0.01% as add-on, DeGrain is higher than 1.0%, and processing characteristics and plasticity worsen.
Played deoxidation and improved corrosion proof effect in the Si adding steel.Be lower than 0.01% content DeGrain.After content surpassed 1.0%, processibility and toughness worsened.
The adding of Cr makes the intensity and the anti-CO of steel 2, Cl -Corrosive nature improves.But Cr content was less than 0.5% o'clock, and solidity to corrosion improves not obvious.Be higher than 5.0wt%, the processibility variation, material cost improves.Cr content generally is controlled at 0.5～5.0%.
Mn is the necessary element of obdurability that improves steel, and is less less than effect in 0.1% o'clock.After Mn content surpasses 2%, anti-CO 2Corrodibility descends.
Al has played desoxydatoin in steel, also improved the stability and the solidity to corrosion of corrosion surface rete in addition.When add-on is lower than 0.001%, DeGrain, add-on surpasses 0.10%, the mechanical property variation.
Cu is anti-CO 2The one of the chief elements that corrosive nature improves, add-on is lower than 0.05%, and DeGrain is higher than 2%, the hot workability variation.
The adding of Ni has improved the hot workability and the corrosion resistance of material.Add-on is lower than 0.05%, and DeGrain surpasses 1.0%, poor processability.
Rare earth: the rare earth of adding has improved the The Nomenclature Composition and Structure of Complexes of surface corrosion film as the surface modification element, thereby has improved the anti-CO of steel 2Corrosive nature.But add-on is lower than 0.005%, and DeGrain surpasses 0.25%, can worsen its mechanical property.
Steel alloy of the present invention is compared with the steel that the patent No. is respectively EP 995809 and WO99/41422.The Cr that wherein contains more content in the composition of EP995809 patent steel, high quality steel category in belonging to, and the selected CO of this steel grade 2The corrodibility of test(ing) medium is lighter than the present invention.Steel alloy interalloy content of the present invention especially Cr content has reduction significantly by comparison, and cost of alloy is lower, belongs to the low-carbon low-alloy steel category; In addition, steel of the present invention is special in behind a small amount of Mo of compound adding and the W, and the solidity to corrosion of steel is greatly improved, at Cl -Content surpasses 10% compound CO 2There is not local corrosion to take place under the corrosive medium situation yet.And Cr content is between 2.1～5.0% among the patent WO99/41422, and than steel height of the present invention, and its solidity to corrosion has a more substantial increase after adding W and rare earth in the steel of the present invention.Meanwhile, original invention steel also has bigger difference with the present invention on manufacture method, it be by quench or tempering after again low-temperaturetempering finally obtain martensitic stucture.And the final tissue of steel of the present invention is a sorbite.
Steel of the present invention is through smelting, forging, rolling, proper heat treatment and meet the performance requriements of API 5CT of N80 level steel through Mechanics Performance Testing after, respectively at CO 2Carry out the corrosion simulated simultaneous test of autoclave in the typical corrosive environment in the oil field, Tarim Basin that corrosion is comparatively given prominence to, test-results shows, year erosion rate of design steel grade has reduced 5-15 times than steel pipes such as N80, the C90 of the present use in oil field, P110 and has not waited, and the local corrosion phenomenon is eliminated.
Embodiment
The chemical ingredients of table 1 expression invention steel and contrast steel, wherein A1-A7 is a steel of the present invention, B1-B3 is the contrast steel.
The chemical ingredients of table 1 invention steel and contrast steel, wt%
Classification Chemical ingredients (wt%) Tissue
?C ?Si ?Mn ??Cr ??Mo ??Cu ??Ni ??W Rare earth ???Al Sorbite
Steel of the present invention A1 ?0.15 ?0.15 ?1.20 ??1.00 ??0.15 ??1.00 ??0.48 ???0.06 Sorbite
A2 ?0.20 ?0.17 ?1.30 ??0.96 ??0.18 ??0.98 ??0.52 ???0.08 Sorbite
A3 ?0.19 ?0.16 ?1.25 ??0.98 ??0.20 ??0.89 ??0.42 ??0.10 ??0.01 ???0.06 Sorbite
A4 ?0.18 ?0.18 ?1.10 ??1.02 ??0.21 ??0.90 ??0.45 ??0.08 ??0.01 ???0.08 Sorbite
A5 ?0.21 ?0.15 ?1.00 ??2.02 ??0.17 ??0.95 ??0.48 ??0.005 ???0.05 Sorbite
A6 ?0.15 ?0.20 ?1.20 ??2.05 ??0.16 ??1.02 ??0.50 ??0.005 ???0.07 Sorbite
A7 ?0.20 ?0.21 ?1.05 ??0.95 ??0.15 ??1.05 ??0.45 ??0.12 ???0.05 Sorbite
The contrast steel B1 ?0.25 ?0.25 ?1.61 ??0.05 ???0.030 Sorbite
B2 ?0.05 ?0.27 ?1.10 ??4.02 ???0.017 Martensite
B3 ?0.13 ?0.22 ?0.99 ??8.55 ??0.46 ???0.046 Martensite
Intensity, unit elongation, hardness value that the test steel obtains after smelting, forging, rolling, thermal treatment are shown in Table 2.As can be seen, the invention steel contains CO in the oil field 2, Cl -Anti-local corrosion performance under the environment obviously is better than contrasting steel, and uniform corrosion speed also has obvious reduction.
The field test condition is Na ++ K +: 17183.69mg/L, HCO 3 -: 122.04mg/L,
Cl -: 33687mg/L, SO 4 2-: 1440.9mg/L, Fe 2+: 100mg/L, Fe 3+: 30mg/L, Ca 2+: 1603.2mg/L, Mg 2+: 641.5mg/L, PH=6.0, test temperature: 110 ℃, CO 2Dividing potential drop: 2.0Mpa, flow velocity: 1.5m/s.
Zero: showing does not have local corrosion; *: showing has local corrosion
The mechanical property and the corrosive nature of table 2 test steel
Grade of steel ????σ b? ????Mpa ??σ 0.5? ??Mpa ????δ 50.8? ????％ ???HRC Oil field CO 2、Cl -Under the environment
Local corrosion Corrosion speed
??A1 ????822 ??655 ????19.0 ???22.0 ????○ ??3.3mm/y
??A2 ????835 ??645 ????18.5 ???21.8 ????○ ??2.5mm/y
??A3 ????840 ??636 ????18.5 ???22.6 ????○ ??0.5mm/y
??A4 ????822 ??622 ????19.5 ???23.9 ????○ ??0.4mm/y
??A5 ????856 ??651 ????20.2 ???23.5 ????○ ??1.2mm/y
??A6 ????832 ??635 ????21.0 ???20.7 ????○ ??1.4mm/y
??A7 ????830 ??620 ????22.0 ???22.5 ????○ ??1.5mm/y
??B1 ????789 ??602 ????20.0 ???22.3 ????× ??45mm/y
??B2 ????820 ??618 ????17.5 ???20.5 ????× ??6mm/y
??B3 ????832 ??620 ????16.5 ???21.4 ????× ??5m/y

Claims (5)

1, the low alloy steel of carbon dioxide corrosion-resistant contains:
C：?0.01～0.30％???Si：0.10～1.0％
Mn：0.10～2.0％????Cr：0.50～5.0％
Mo：0.01～1.0％????Cu：0.05～2.0％
Ni：0.05～1.0％????Al：0.005～0.1％；
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
2, the low alloy steel of carbon dioxide corrosion-resistant contains:
C：?0.01～0.30％???Si：0.10～1.0％
Mn：0.10～2.0％????Cr：0.50～5.0％
Mo：0.01～1.0％????Cu：0.05～2.0％
Ni：0.05～1.0％????Al：0.005～0.1％；
Also contain rare earth 0.005～0.25%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
3, the low alloy steel of carbon dioxide corrosion-resistant contains:
C：?0.01～0.30％???Si：0.10～1.0％
Mn：0.10～2.0％????Cr：0.50～5.0％
Mo：0.01～1.0％????Cu：0.05～2.0％
Ni：0.05～1.0％????Al：0.005～0.1％；
Also contain W:0.01～1.0%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
4, the low alloy steel of carbon dioxide corrosion-resistant contains:
C：0.01～0.30％????Si：0.10～1.0％
Mn：0.10～2.0％????Cr：0.50～5.0％
Mo：0.01～1.0％????Cu：0.05～2.0％
Ni：0.05～1.0％????Al：0.005～0.1％；
Also contain rare earth 0.005～0.25%;
Also further contain W:0.01～1.0%;
All the other are that Fe and unavoidable impurities are formed, and it is organized as sorbite, more than all be weight percentage.
5, the low alloy steel as the described carbon dioxide corrosion-resistant of claim 1-4 is used to make oil gas well tubing and casing.
CNB011265752A 2001-08-28 2001-08-28 Carbon dioxide corrosion-resistant low alloy steel and oil casing Expired - Lifetime CN1151305C (en)

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