CN103602903B - High intensity carbon dioxide corrosion-resistant oil well pipe and manufacture method thereof - Google Patents
High intensity carbon dioxide corrosion-resistant oil well pipe and manufacture method thereof Download PDFInfo
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Abstract
High intensity carbon dioxide corrosion-resistant oil well pipe and manufacture method thereof, comprise the steps: 1) to smelt, cast, its chemical component weight percentage ratio is: C0.30～0.42%, Si.10～1.0%, P≤0.015%, S≤0.005%, Mn0.80～1.5%, Cr0.5～1.5%, V0.21～0.4%, Al0.01～0.10%, N0.031～0.05%, remaining is Fe and inevitable impurity, and wherein, V/N Ratio control is 6～11；Using smelting, external refining and vacuum outgas, be casting continuously to form round base, starting tapping temperature during steel-making is 1620～1710 DEG C；2) justifying base soaking in annular furnace, piercing temperature 1200～1240 DEG C, finishing temperature 900～950 DEG C, after hot rolling, steel pipe air cooling is to room temperature；3) hot-rolled pipe uses normalizing process, normalizing temperature 920～960 DEG C, is incubated 30～50min, air cooling after coming out of the stove；The oil well pipe mechanical property obtained reaches more than 95ksi grade of steel, and under room temperature, metallographic structure is ferrite+pearlite+sorbite.
Description
Technical field
The present invention relates to oil well pipe, particularly to high intensity carbon dioxide corrosion-resistant oil well pipe and manufacture method thereof.
Background technology
CO2Corrosion is a kind of common corrosion type generally existed in World Oil Industry, is also puzzlement China oil gas
One of industrial development extremely distinct issues.China Tarim Basin, long celebrating, Sichuan, North China, triumph, Bo Nan, Wenchang etc. are main at present
The highest CO is all contained in power oil field2, the strong corrosive medium such as Cl-, annual oil well pipe is because of CO2The accident that corrosion failure causes is to oil field
The economic loss brought is up to more than hundred million yuan, and the normal safe having had a strong impact on oil field produces.Anticorrosion from material
Angle is seen, in the complex media environment such as high carbonated, chloride ion, salinity, it is ensured that oilfield safety, give birth to efficiently
Producing, maximally effective way is to use expensive modified form 13Cr, the high chromium rust free steel tubing of even more than 22Cr.But
Owing to China's majority oil field belongs to lean ore low permeability oil field, use expensive high chromium-stainless steel oil pipe, oil field one-time investment
Too big, economy is poor.The most most of oil fields have to use general straight carbon steel tubing at present, this thus to result in oil field many
Play serious CO2Corrosion accident.To this end, part producer have developed more than 80ksi grade of steel, need to economical by modifier treatment
The 3Cr anti-CO of series2Corrosion oil annular pipe product.Along with the change of mining conditions, lot of domestic and international chloride ion content is relatively low, original not
Containing CO2Oil/gas Well in occur in that trace amounts of CO2, and the Oil/gas Well developed is deeper, for this situation, uses mesh
The N80 tubing and casing of front oil field routine can not meet anti-CO2The requirement of corrosive nature, and use in current domestic and international market
Universal 3Cr series oil pipe also difficulty reaches optimal cost performance, to this end, domestic a lot of oil field proposes high intensity and is resistant to CO2Rotten
The demand of the cost performance height oil pipe of erosion.Therefore, the micro-anti-CO of high intensity is researched and developed targetedly2Burn into Technology for Heating Processing is more
Add the economical low-alloy oil pipe that simple, cost performance is more suitable for and there is very realistic meaning.
In current technology, relevant anti-CO2Corrosion (or the most anti-CO2And H2S corrodes) have many by the patent of invention of steel alloy
Part, but be that middle alloy or super 13Cr, 15Cr and 22Cr two phase stainless steel etc. are heavy alloyed mostly involved by these patents
Chemical composition, and its manufacture process the most all must use high temperature modifier treatment technique.
The low-alloy steel of Chinese patent CN1401809A carbon dioxide corrosion-resistant and tubing and casing, its C content≤0.3%, mainly
By adding the elements such as suitable Mo, Ni, W, Cr, after conditioned or normalized treatment, obtain the carbon dioxide corrosion-resistant of excellence
Can, its final organization type is sorbite or tempered sorbite.
Chinese patent CN1292429A resistant to carbon dioxide and seawater corrosion low-alloy steel for oil casing pipe, use low carbon component,
Resistant to carbon dioxide and the seawater corrosion performance of alloy is usually improved by adding the units such as suitable Mo, Cr, Cu, through smelting, forging,
After rolling, heat treatment, intensity can reach more than 80ksi grade of steel.
Chinese patent CN1487112A resistant to carbon dioxide and hydrogen sulfide corrosion low-alloy steel, it is mainly characterized by and passes through
80～the 95ksi anti-CO of grade of steel can be manufactured by Tempering and Quenching after adding about 3% Cr and RE elements of Ce2、H2S corrodes oil
Pipe, final organization type is tempered sorbite.
European patent EP 995809A1, mainly by adding the Cr and appropriate Cu and Al of more content, to improve material
Resistant to carbon dioxide and seawater corrosion performance, especially overcome the local corrosion phenomenon under the conditions of particular medium.But this is special
In profit, the addition of alloying element especially Cr is more than 4%, belongs to middle high alloy category, steel pipe relatively costly.Additionally, this is special
Sharp steel alloy is quenched or obtains martensite types of tissue after normalized treatment.
PCT Patent WO9941422 with Mn, Cr as main alloy element, add if desired a small amount of Cu, Ni, Mo, Ti, Nb,
B, product is finally martensite types of tissue.
United States Patent (USP) US6648991, Cr content be 1.5-4.0%, Mn content be 0.3-0.8%, C content is 0.06-0.1%,
Being equipped with suitable Mo, V element, belong to ultra-low-carbon steel scope, after alloy uses hot rolling, hardening and tempering process processes, and gained is organized as tempering
Sorbite type.
Japan Patent JP2001059136 is mainly by adding the Cr and appropriate B of more content and passing through Tempering and Quenching
Rear acquisition tempered sorbite tissue, to meet anti-CO2Corrosion and H2S corrosive nature.
Japan Patent JP2000063994 mainly by adding the Cr of more content, and add when necessary a small amount of Cu,
The elements such as V, W, Mo, and by obtaining tempered sorbite tissue after Tempering and Quenching, reach anti-CO2Corrosion and H2S corrosiveness.
Also partial monopoly is had to propose without using the Technology for Heating Processing such as quenched to produce the anti-corruption of ferrite+pearlitic structrure
Erosion tubing and casing, such as Chinese patent 201110385611.9 produce, by microalloying, the low-alloy that intensity level is 80ksi
Tubing and casing, but due to the restriction of ferrite+pearlitic structrure, intensity level is relatively low, does not reaches oil field deep well exploitation required
Yield strength in 95ksi and above requirement of strength.
Summary of the invention
It is an object of the invention to provide a kind of high intensity carbon dioxide corrosion-resistant oil well pipe and manufacture method thereof, it is
The anti-CO of high intensity more than 95ksi grade of steel2With chloride ion corrosion oil annular tube low-alloy steel.
For reaching above-mentioned purpose, the technical scheme is that
The present invention is designed by microalloying ingredient, utilize V and N precipitating reinforcing effect improve the strength of materials, simultaneously V and
N at high temperature matrix is to form tiny precipitate when of austenite, can be as group during follow-up phase in version
The core that when knitting transformation, ferritic structure is formed, promotes the formation of the ferritic structure of fine uniform, relies on its refined crystalline strengthening
Effect improves the strength of materials, and is organized as ferrite+pearlite+sorbite after ensureing phase transformation, it is suppressed that bainite and geneva
The formation of the tissue such as body.Ferrite+pearlitic structrure hardness and intensity owing to being formed in conventional material are relatively low, are extremely difficult to
More than 80ksi intensity level, is therefore designed by V, N, Nb microalloying, relies on precipitation strength, phase transformation strengthening and refined crystalline strengthening
Improving the intensity of material, the intensity reaching the requirement of deep-well tubing and casing reaches more than 95ksi.
Specifically, the high intensity carbon dioxide corrosion-resistant oil well pipe of the present invention, its chemical component weight percentage ratio is: C:
0.30～0.42%, Si:0.10～1.0%, Mn:0.80～1.5%, Cr:0.5～1.5%, V:0.21～0.4%, Al:0.01～
0.10%, N:0.031～0.05%, remaining is Fe and inevitable impurity, and wherein, V/N ratio range controls 6～11.
In present component designs:
C:C is carbide former, can improve the intensity of steel, and DeGrain time the lowest can significantly drop time the highest
The welding performance of low steel.
Si:Si is solid-solution in the ferrite yield strength with raising steel, unsuitable too high, and the highest meeting makes processing and toughness deteriorate,
Less than 0.1% DeGrain.
Mn:Mn is austenite former, can improve the quenching degree of steel, acts on inconspicuous, contain when content is less than 0.8%
When amount is more than 1.5%, the microstructure segregation in steel will be dramatically increased, affect uniformity and the impact property of hot rolling microstructure.
Cr: the strong quenching degree element that improves, carbide, during tempering, carbide precipitate improves the intensity of steel,
But separate out thick M23C6 carbide during too high levels, reduce toughness, by weight percentage, preferably use content 0.5-1.5%.
V:V can crystal grain thinning, form carbide, the intensity of steel can be significantly improved, but when content reaches too high, to significantly
Reduce toughness index.
N:N is precipitation strength element, forms the nitride of Nb, V during cooling, plays the effect improving intensity.
P, S:P and S are the objectionable impurities elements in steel, the toughness of too high levels meeting steel, therefore should reduce in steel as far as possible
P, S content.
The present invention relies on precipitation strength effect and the refined crystalline strengthening effect of the precipitate generation of V and N element formation, thus reaches
It is beyond one's reach intensity level to general ferrite+pearlite+sorbite.Owing to V and N variable concentrations proportioning can appreciable impact
Precipitating reinforcing effect, if V and N content ratio are higher, matrix is that high temperature austenite phase time only has fraction V element and N
Element combines and forms precipitate, and remaining V forms precipitate with C element during follow-up low temperature phase change, can significantly improve
Intensity, so makes ferrite forming core particle in phase transition process and reduces, thus reduce ferritic content, cause toughness to reduce,
(ideal format this type oil well pipe ballistic work API standard requires for the requirement of oil well pipe toughness to be difficult to meet API standard
More than 20J)；If V and N content ratio are relatively low, matrix is that high temperature austenite phase time major part V element is combined with N element
Form precipitate, reduce V during follow-up low temperature phase change, form precipitation strength work produced by precipitate with C element
With, cause intensity to reduce, it is difficult to (95ksi oil well pipe yield strength requires to the requirement of intensity to meet high-strength corrosion-resistant pipe
655-862MPa).
Therefore, lot of experiments is passed through, it is determined that V content and N content ratio range control at 6-11, its intensity and tough
Property index can reach the performance requirement of 95ksi carbon dioxide corrosion-resistant pipe.
It addition, Cr element has close pass to tissue and the corrosion resistance of the performance of 95ksi carbon dioxide corrosion-resistant pipe
System, Cr can improve quenching degree and the carbon dioxide corrosion-resistant performance of material, and Cr content is higher than 1.5%, and quenching degree is higher, easily
Produce bainite structure；Cr content is less than 0.5%, carbon dioxide corrosion-resistant poor-performing.
The manufacture method of the high intensity carbon dioxide corrosion-resistant oil well pipe of the present invention, comprises the steps:
1) smelt, cast
High intensity carbon dioxide corrosion-resistant oil well pipe, its chemical component weight percentage ratio is: C:0.30～0.42%, Si:
0.10～1.0%, P≤0.015%, S≤0.005%, Mn:0.80～1.5%, Cr:0.5～1.5%, V:0.21～0.4%, Al:
0.01～0.10%, N:0.031～0.05%, remaining is Fe and inevitable impurity, wherein, V/N ratio range control 6～
11；Smelt by mentioned component, external refining and vacuum outgas, be casting continuously to form round base, start during steel-making tapping temperature be 1620～
1710℃；Pulling speed of continuous casting controls at below 2.1m/min, and banded segregation controls within 2 grades；
2) justifying base soaking in annular furnace, piercing temperature 1200～1240 DEG C, finishing temperature 900 DEG C～950 DEG C, after hot rolling
Steel pipe air cooling is to room temperature；
3) hot-rolled pipe use normalizing process, normalizing process of thermal treatment is: normalizing temperature 920～960 DEG C, insulation 30～
50min, air cooling after coming out of the stove.
Steel of the present invention is after steel-making, hot rolling and normalizing heat treatment, and mechanical property has reached more than 95ksi grade of steel, under room temperature
This material final metallographic structure type is that ferrite+pearlite+sorbite is to ensure corrosion resistance.
In manufacture method of the present invention, positive heat treat temperatures is less than 920 DEG C, and the precipitate of V and N dissolves in austenite
Spending relatively low, it is difficult to separate out the precipitate of fine uniform in follow-up process air cooler, intensity can not meet the requirement of 95ksi, just
Fire temperature, higher than 960 DEG C, forms a large amount of bainite structure, it is impossible to obtain ferrite+pearly-lustre in the process air cooler that normalizing is follow-up
Body+sorbite tissue, corrosion resistance reduces.
Beneficial effects of the present invention:
General rust-proof oil casing product mostly is and is applicable to containing medium or higher CO2In the Oil/gas Well of content, manufacture process
In generally require after hot-rolled process and ensure carbon dioxide corrosion-resistant performance by the heat treatment mode that high temperature is quenched, i.e. in Austria
After family name's body temperature temperatures above shrend or oil quenching, the most long-time tempering reaches performance requirement, its main production
Flow process is steel-making continuous casting tube rolling Tempering and Quenching, and final organization type is tempered sorbite.
And steel making technique of the present invention is relatively easy, uses normalizing process to process after hot rolling, simplify Technology for Heating Processing, joint
Save cost.Its technological process of production is steel-making continuous casting tube rolling normalizing, and final organization type is ferrite+pearlite
Tissue+sorbite tissue, metallographic structure is as shown in Figure 1.
The tubing and casing with normalizing state pearlite+ferrite+sorbite tissue breaches simple dependence alloying element raising
The traditional design principle of corrosion resistance, uses heterogeneous structure corrosion rate and different raisings of surface topography in corrosion process
The adhesion of corrosive film and compactness, thus improve corrosion resistance.Pearlite+ferrite+sorbite three-phase contexture is due to it
Corrosion rate difference makes specimen surface uneven so that form CO in corrosion process2The FeCO that corrosion produces3Layer can be good
Be attached on metallic matrix, effect is more preferable compared with ferrite+pearlite two-phase structure.Meanwhile, ferritic along with matrix surface
Corrosion, pearlite in normalized structure and sorbite corrosion produce cemetite lamellae Rotating fields, and sheet interlayer spacing is not of uniform size and
Direction is different, it is possible to surely prick corrosive film, thus improve corrosive film compactness and and metallic matrix between adhesion, this just makes
Fire state three-phase contexture corrosion layer in anaclisis, film forming speed and growth than ferrite+pearlite two-phase structure and quenched and tempered state
Tissue is more beneficial for resisting CO2With the corrosion of chloride ion, after three-phase contexture corrosion, microscopic appearance is as shown in Figure 2.
More than the 95Ksi grade of steel of mentioned component and manufacture method production is used to have normalizing state pearlite+ferrite+Soxhlet
The anti-CO of soma's tubing and casing2With chloride ion corrosion performance being more than doubled than conventional API N80 oil pipe.
Accompanying drawing explanation
Fig. 1 is the metallographic structure of the embodiment of the present invention 4 steel.
Fig. 2 is pattern after corrosion sample surface clean.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Table 1 show the composition of embodiment of the present invention steel, and table 2 is embodiment of the present invention technique, and table 3 is the power of embodiment steel
Learn performance, corrosive nature.
Wherein, comparative example 1 is below 80ksi low-intensity carbon dioxide corrosion-resistant steel, and V/N ratio range controls 6～11,
Comparative example 2 be at present conventional 95ksi Oil sleeve steel ball B3-B4 be [V]/[N] ratio beyond the scope of this invention (V/N ratio 6～
11) comparative example steel grade time, is all the N80 oil pipe commonly used at present of oil field.
Embodiment steel and comparative example steel production process key process parameter be briefly: starting tapping temperature during steel-making is 1620
～1710 DEG C；Pulling speed of continuous casting controls at below 2.1m/min, piercing temperature 1200～1240 DEG C, finishing temperature 900 DEG C～950
DEG C, concrete technology is shown in Table 2.After hot rolling, steel pipe air cooling is to room temperature, normalizing temperature 920～960 DEG C, is incubated 30～50min, respectively implements
Example technique is as shown in table 1.
Table 1 unit: percentage by weight
| C | Si | Mn | Cr | V | Al | N | P | S | |
| Embodiment 1 | 0.30 | 0.10 | 0.80 | 1.5 | 0.21 | 0.02 | 0.035 | 0.015 | 0.005 |
| Embodiment 2 | 0.35 | 0.70 | 0.90 | 1.2 | 0.31 | 0.05 | 0.031 | 0.010 | 0.003 |
| Embodiment 3 | 0.35 | 0.20 | 0.85 | 1.8 | 0.25 | 0.02 | 0.028 | 0.008 | 0.001 |
| Embodiment 4 | 0.38 | 0.50 | 1.40 | 1.5 | 0.30 | 0.03 | 0.030 | 0.005 | 0.002 |
| Embodiment 5 | 0.39 | 0.89 | 1.20 | 1.0 | 0.35 | 0.08 | 0.050 | 0.012 | 0.004 |
| Embodiment 6 | 0.42 | 1.00 | 1.50 | 0.5 | 0.40 | 0.04 | 0.036 | 0.013 | 0.002 |
| Comparative example 1 | 0.38 | 0.89 | 1.28 | 1.14 | 0.10 | 0.08 | 0.012 | 0.009 | 0.003 |
| Comparative example 2 | 0.32 | 0.31 | 1.5 | — | — | — | 0.006 | 0.006 | 0.002 |
| Comparative example 3 | 0.30 | 0.10 | 0.8 | 1.5 | 0.21 | 0.02 | 0.050 | 0.015 | 0.005 |
| Comparative example 4 | 0.39 | 0.89 | 1.2 | 1 | 0.35 | 0.08 | 0.031 | 0.012 | 0.004 |
Table 2
Each embodiment mechanical property:
According to GB6397-86 method, measure steel of the present invention and the yield strength of comparative example steel, tensile strength and ballistic work etc.
Mechanical property, it the results are shown in Table 3.
Each embodiment is at oil field CO2、Cl-Corrosive nature under environment:
It is Na at experimental condition++K+: 35000mg/L, HCO3 -: 81mg/L, Cl-: 36000mg/L, SO4 2-: 111mg/L,
Ca2+: 890mg/L, Mg2+: 150mg/L, PH=6.6, test temperature: 90 DEG C, CO2Dividing potential drop: 0.5MPa, flow velocity: measure under 1.5m/s
Steel of the present invention and the corrosive nature of comparative example steel, it the results are shown in Table 3.
Table 3 tests the mechanical property of steel, corrosive nature
The steel alloy of the embodiment of the present invention, after smelting, forging, hot rolling or normalized treatment, meets through Mechanics Performance Testing
95ksi grade of steel (corresponding SMYS the is 655-862MPa) performance requirement (shown in table 3) of API5CT standard, is organized as pearl
Body of light+ferrite+sorbite.
Comparative example 1 intensity is unable to reach 95ksi requirements above, and corrosion resistance is on the low side, comparative example 2 intensity and anticorrosive
Performance is the most poor, and tissue does not reaches ferrite+pearlite+sorbite organizational requirements, and [V] of comparative example 3 steel grade/[N] ratio is relatively
Low, intensity does not reaches more than 95ksi requirement of strength, and [V] of comparative example 4 steel grade/[N] ratio is higher, and ballistic work does not reaches standard
Requirement.
The actual etching condition in certain oil field (condition as described in Example 2) is used to carry out the corrosion simulated contrast test of autoclave,
Result of the test shows, the 95ksi conventional oil sleeve pipe that the corrosion resistance of the alloy steel grade of the present invention is currently used compared with oil field improves
More than 1 times.
The steel alloy of the present invention may be used for deep-well and contains the hole condition of carbon dioxide corrosion medium, its successful design and opening
Send out and will bring great economic benefit, wide market.
Claims (2)
1. high intensity carbon dioxide corrosion-resistant oil well pipe, its chemical component weight percentage ratio is: C:0.30～0.42%, Si:0.10
～1.0%, P≤0.015%, S≤0.005%, Mn:0.80～1.5%, Cr:0.5～1.5%, V:0.21～0.4%, Al:0.01～
0.10%, N:0.031～0.05%, remaining is Fe and inevitable impurity, and wherein, V/N ratio range controls 6～11, should
Oil well pipe mechanical property reaches more than 95ksi grade of steel, and under room temperature, final metallographic structure type is ferrite+pearlite+Soxhlet
Body.
2. the manufacture method of high intensity carbon dioxide corrosion-resistant oil well pipe as claimed in claim 1, comprises the steps:
1) smelt, cast
High intensity carbon dioxide corrosion-resistant oil well pipe, its chemical component weight percentage ratio is: C:0.30～0.42%, Si:0.10～
1.0%, P≤0.015%, S≤0.005%, Mn:0.80～1.5%, Cr:0.5～1.5%, V:0.21～0.4%, Al:0.01～
0.10%, N:0.031～0.05%, remaining is Fe and inevitable impurity, and wherein, V/N ratio range controls 6～11；Press
Mentioned component smelting, external refining and vacuum outgas, be casting continuously to form round base, and starting tapping temperature during steel-making is 1620～1710 DEG C；
Pulling speed of continuous casting controls at below 2.1m/min；
2) base soaking in annular furnace is justified, piercing temperature 1200～1240 DEG C, finishing temperature 900 DEG C～950 DEG C, steel pipe after hot rolling
Air cooling is to room temperature；
3) hot-rolled pipe uses normalizing process, normalizing temperature 920～960 DEG C, is incubated 30～50min, air cooling after coming out of the stove；The oil obtained
Well casing mechanical property reaches more than 95ksi grade of steel, and under room temperature, final metallographic structure type is ferrite+pearlite+sorbite.
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| CN104789882A (en) * | 2015-03-16 | 2015-07-22 | 天津欧派卡石油管材有限公司 | Production method of petroleum casing pipe |
| CN107287499B (en) * | 2016-03-31 | 2019-05-31 | 鞍钢股份有限公司 | A kind of high temperature resistant thermal production well oil well pipe and its manufacturing method |
| CN107557661B (en) * | 2016-06-30 | 2019-06-28 | 鞍钢股份有限公司 | It is a kind of economical with corrosion resistance J55 seamless pipe and its manufacturing method |
| CN108004461B (en) * | 2016-10-31 | 2019-11-22 | 宝山钢铁股份有限公司 | A kind of tubing and casing and its manufacturing method of carbon dioxide corrosion-resistant |
| CN108624810B (en) * | 2017-06-26 | 2020-06-23 | 宝山钢铁股份有限公司 | Low-cost high-strength high-sulfur-resistance oil well pipe and manufacturing method thereof |
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| CN101928888A (en) * | 2009-06-23 | 2010-12-29 | 宝山钢铁股份有限公司 | Low-alloy steel for resisting carbon dioxide corrosion and manufacturing method thereof |
| CN102400057A (en) * | 2011-11-28 | 2012-04-04 | 宝山钢铁股份有限公司 | Low-alloy steel used for oil well pipe with carbon dioxide corrosion resistance and manufacturing method thereof |
| CN102618784A (en) * | 2012-03-22 | 2012-08-01 | 宝山钢铁股份有限公司 | 60kg-level low-cost and high-toughness steel plate and production method thereof |
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| JPH10324946A (en) * | 1997-05-27 | 1998-12-08 | Komatsu Ltd | High strength non-heat treated steel for steel tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101928888A (en) * | 2009-06-23 | 2010-12-29 | 宝山钢铁股份有限公司 | Low-alloy steel for resisting carbon dioxide corrosion and manufacturing method thereof |
| CN102400057A (en) * | 2011-11-28 | 2012-04-04 | 宝山钢铁股份有限公司 | Low-alloy steel used for oil well pipe with carbon dioxide corrosion resistance and manufacturing method thereof |
| CN102618784A (en) * | 2012-03-22 | 2012-08-01 | 宝山钢铁股份有限公司 | 60kg-level low-cost and high-toughness steel plate and production method thereof |
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