CN103820713B - The anti-H of high-intensity high-tenacity2the preparation method of S corrosion oil pipe - Google Patents
The anti-H of high-intensity high-tenacity2the preparation method of S corrosion oil pipe Download PDFInfo
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Abstract
The invention discloses a kind of anti-H of high-intensity high-tenacity2The preparation method of S corrosion oil pipe, including: STEELMAKING PRODUCTION, the rolling of steel and roll state steel heat treatment.The anti-H of high-intensity high-tenacity of the present invention2S corrosion oil pipe has higher anti-H2S corrosive nature.
Description
Technical field
The present invention relates to metal material field, specifically, relate to a kind of anti-H of high-intensity high-tenacity2The preparation method of S corrosion oil pipe.
Background technology
In domestic and international oil field, about 1/3 containing hydrogen sulfide gas, the oil-gas Layer in the oil fields such as China's many oil fields such as Sichuan, long celebrating, North China, Xinjiang, Jiang-Han Area all contains hydrogen sulfide, wherein Sichuan oilfield is particularly acute, and it is reported that Sichuan oilfield is that one of the most serious oil gas field is corroded in the whole world.Abroad also there are many hydrogen sulfide containing oil fields, such as the Barrow house oil field of the U.S., your oil field, gulf of Canadian truncation etc..Ordinary casing is when exploiting for hydrogen sulfide containing petroleum resources, oil pipe is under using the effect of stress and hydrogen sulfide gas, often there is suddenly brittle failure when stress is far below itself yield strength, this phenomenon is referred to as H 2 S stress corrosion, the lighter causes casing string or whole mouth well to scrap, severe one can cause blowout, makes hydrogen sulfide the most excessive with oil gas, causes whole bench drill machine and the considerable damage of ecological environment around.Therefore, exploit hydrogen sulfide containing petroleum resources to be necessary for using anti-H 2 S sleeve pipe.
High strength sulfur resisting another hang-up of hydrogen-type corrosion oil pipe is exactly, and increases or do not reduce impact flexibility while how improving yield strength.It is known that in low-carbon and low-alloy quenched and tempered steel, yield strength and impact flexibility are the contradictory relations risen that disappears each other, say, that yield strength improves, inevitable, its impact flexibility will reduce.Obtain higher yield strength, be necessary for reducing quenched during temperature, now impact flexibility then reduces with the reduction of temperature, if it is desired to improve the impact flexibility of steel, then must be tempered at a higher temperature, now the yield strength of material then declines to a great extent.
Summary of the invention
The technical problem to be solved is to provide a kind of anti-H of high-intensity high-tenacity2S corrodes oil pipe, has good corrosion resistance.
Technical scheme is as follows:
A kind of anti-H of high-intensity high-tenacity2S corrodes oil pipe, the weight/mass percentage composition of its material chemical composition includes: C 0.158%～0.167%, Si 0.298%～0.322%, Mn 0.499%～0.514%, Cr 0.98%～1.12%, Mo 0.377%～0.405%, P≤0.018%, S≤0.01%, V 0.051%～0.054%, Ti 0.011%～0.017%, Al 0.016%～0.021%, remaining is Fe, and mass fraction amounts to 100%.
Further, the anti-H of described high-intensity high-tenacity2The weight/mass percentage composition of the chemical composition of S corrosion oil pipe includes: C 0.164%, Si 0.317%, Mn 0.514%, Cr 1.12%, Mo 0.398%, P 0.018%, S 0.010%, V 0.051%, Ti 0.011% and Al 0.021%；Or, C 0.160%, Si 0.322%, Mn 0.504%, Cr 1.02%, Mo 0.386%, P 0.015%, S 0.008%, V 0.054%, Ti 0.015% and Al 0.020%；Or, C 0.158%, Si 0.305%, Mn 0.501%, Cr 0.98%, Mo 0.377%, P 0.012%, S 0.009%, V 0.052%, Ti 0.017% and Al 0.019%；Or, C 0.167%, Si 0.298%, Mn 0.499%, Cr 1.10%, Mo 0.405%, P 0.017%, S 0.008%, V 0.053%, Ti 0.014% and Al 0.016%.
Another technical problem to be solved by this invention is to provide a kind of anti-H of high-intensity high-tenacity2The preparation method of S corrosion oil pipe, can prepare the anti-H of high-intensity high-tenacity with good corrosion resistance2S corrodes oil pipe.
Another technical scheme of the present invention is as follows:
A kind of anti-H of high-intensity high-tenacity2The preparation method of S corrosion oil pipe, including: STEELMAKING PRODUCTION, the rolling of steel and roll state steel heat treatment, the anti-H of high-intensity high-tenacity prepared2The weight/mass percentage composition of the material chemical composition of S corrosion oil pipe includes: C 0.158%～0.167%, Si 0.298%～0.322%, Mn 0.499%～0.514%, Cr 0.98%～1.12%, Mo 0.377%～0.405%, P≤0.018%, S≤0.01%, V 0.051%～0.054%, Ti 0.011%～0.017%, Al 0.016%～0.021%, remaining is Fe, and mass fraction amounts to 100%.
Further, described STEELMAKING PRODUCTION includes: molten iron pretreatment, converter smelting, LF refine, VD vacuum outgas and round billet continuous casting.
Further, described converter smelting uses desulphurised hot metal to smelt, every stove molten iron is 100 tons, every stove molten iron adds ferrosilicon 350kg, ferromanganese 850kg, ferrochrome 2000kg, molybdenum-iron 880kg, vanadium iron 100kg, ferrotianium 50kg, the weight/mass percentage composition of the composition of the molten iron of the terminal of described converter smelting includes: C >=0.06%, P≤0.015%, and described converter smelting uses single slag technique to smelt, before tapping, every stove molten iron adds 200kg white lime slag making, finishing slag basicity >=3.0；Described LF refine carries out slag making desulfurization, composition adjustment and warming temperature according to molten steel composition and the temperature of converter smelting, and slag former is CaO-CaF2Molten steel per ton adds 8-10kg slag former, adjust molten steel composition by following weight/mass percentage composition to include: C 0.16%, Si 0.30%, Mn 0.50%, Cr 1.0%, Mo 0.40%, P≤0.02%, S≤0.015%, V 0.052%, Ti 0.015%, Al 0.02%, the target temperature of warming temperature is 1536 DEG C；Vacuum≤the 0.06KPa of described VD vacuum outgas, deep vacuum time >=13min, soft blow Ar >=10min；The constant pulling rate of described round billet continuous casting is 1m/min, molten steel overheat Δ T≤30 DEG C.
Further, the rolling of described steel specifically includes that the heating of round base, perforation, tube rolling and stretch reducing.
Further: the temperature of described round base heating is 1250～1270 DEG C, and the temperature of described perforation is 1180～1250 DEG C, and the temperature of described tube rolling is 1020～1150 DEG C, and the temperature of described stretch reducing is 750～820 DEG C.
Further: described in roll state steel heat treatment include quenching and tempering, the temperature of described quenching is 920 ± 10 DEG C, 920 ± 10 DEG C be incubated 65～70 minutes；The temperature of described tempering is 680 ± 10 DEG C, is incubated 70～80 minutes at 680 ± 10 DEG C.
Further, the anti-H of described high-intensity high-tenacity prepared2The weight/mass percentage composition of the material chemical composition of S corrosion oil pipe includes: C 0.164%, Si 0.317%, Mn 0.514%, Cr 1.12%, Mo 0.398%, P 0.018%, S 0.010%, V 0.051%, Ti 0.011% and Al 0.021%；Or, C 0.160%, Si 0.322%, Mn 0.504%, Cr 1.02%, Mo 0.386%, P 0.015%, S 0.008%, V 0.054%, Ti 0.015% and Al 0.020%；Or, C 0.158%, Si 0.305%, Mn 0.501%, Cr 0.98%, Mo 0.377%, P 0.012%, S 0.009%, V 0.052%, Ti 0.017% and Al 0.019%；Or, C 0.167%, Si 0.298%, Mn 0.499%, Cr 1.10%, Mo 0.405%, P 0.017%, S 0.008%, V 0.053%, Ti 0.014% and Al 0.016%.
The technique effect of the present invention is as follows:
1, the anti-H of the high-intensity high-tenacity of the present invention2The chemical composition of the material of S corrosion oil pipe rationally makes the anti-H of high-intensity high-tenacity2S corrosion oil pipe has higher anti-H2S corrosive nature.
2, the present invention use refined crystalline strengthening and precipitation strength technology make material have high intensity and high tenacity, reasonably smelt continuous casting process, rolling mill practice, Technology for Heating Processing make product have higher exploitativeness.
3, the anti-H of high-intensity high-tenacity that the present invention provides2The anti-H of high-intensity high-tenacity that the preparation method of S corrosion oil pipe obtains2The quality of S corrosion oil pipe is good, and production efficiency is high, low cost so that material energy-saving environmental protection, good in economic efficiency, is suitable for large-scale production, has good marketing using value.
Detailed description of the invention
From the market demand and technical barrier, the present invention devises rational chemical composition by the effect in the material of each element, produce intensity be up to 110psi grade of steel by smelting continuous casting, rolling, hardening and tempering process, impact flexibility is higher than API 5CT standard-required, and the anti-H of high-intensity high-tenacity that corrosion resistance is good2S corrodes oil pipe.The anti-H of high-intensity high-tenacity of the present invention2Specifically comprising the following steps that of the preparation method of S corrosion oil pipe
Step S1: STEELMAKING PRODUCTION
STEELMAKING PRODUCTION includes: molten iron pretreatment, converter smelting, LF refine, VD vacuum outgas and round billet continuous casting.Steelmaking process uses nitrogen fixation technology, deoxy technology, clean steel technology to make blank have good quality.
By molten iron pretreatment, molten iron is carried out pre-desulfurization so that sulfur weight/mass percentage composition controls below 0.3%.
Converter smelting uses desulphurised hot metal, for non-metallic inclusion in suppression material, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron, vanadium iron and ferro-titanium necessary deoxidation alloying before addition, addition calculates according to composition design content requirement in alloy content, steel in its recovery rate, ferrous alloy.Every stove molten iron is 100 tons, and the every stove of ferrosilicon adds 350kg, the every stove of ferromanganese adds 850kg, the every stove of ferrochrome adds 2000kg, the every stove of molybdenum-iron adds 880kg, the every stove of vanadium iron adds 100kg, the every stove of ferrotianium adds 50kg.Owing to gas content such as oxygen nitrogen in material can be made while carburetting to increase, therefore the control target of the weight/mass percentage composition of the composition of the molten iron of converter terminal includes: C >=0.06%, P≤0.015%.Using single slag technique to smelt, before tapping, every stove molten iron adds 200kg white lime slag making, finishing slag basicity >=3.0.For ensureing the cleanliness factor of material, necessary pushing off the slag during tapping, pushing off the slag unsuccessfully must be skimmed.
In LF refine link, carry out slag making desulfurization, composition adjustment and warming temperature according to converter molten steel composition and temperature.Slag former uses CaO-CaF2Molten steel per ton adds 8-10kg slag former, the desired value adjusting molten steel composition by following weight/mass percentage composition includes: C 0.16%, Si 0.30%, Mn 0.50%, Cr 1.0%, Mo 0.40%, P≤0.018%, S≤0.01%, V 0.052%, Ti 0.015%, Al 0.02%, the target temperature of warming temperature is 1536 DEG C.
The deep vacuum desired value≤0.06KPa of VD vacuum outgas, deep vacuum time >=13 minute, soft blow Ar >=10 minute, to ensure gas content relatively low in material.
Round billet continuous casting process uses electromagnetic agitation technique, and constant casting speed control is in 1m/min, molten steel overheat Δ T≤30 DEG C.Use way of stacking to cool down, air port should be avoided simultaneously.
Step S2: the rolling of steel
The rolling of steel specifically includes that the heating of round base, perforation, tube rolling and stretch reducing, and detailed process is: circle base → sawing → circle base heating → perforation → tube rolling → stretch reducing → cooling → crop end → align → check → pack → weigh → put in storage.Application Ф 159MPM unit rolling specs is the seamless steel pipe of Φ 73.02mm × 5.51mm, by laboratory thermal modeling test, the rolling mill practice that optimization is optimal, concrete rolling mill practice is heated to 1250～1270 DEG C for circle base in rotary heating furnace, the temperature of circle base perforation is 1180～1250 DEG C, the temperature of tube rolling is 1020～1150 DEG C, and the temperature of stretch reducing is 750～820 DEG C.This rolling mill practice ensure that the lumber recovery of seamless steel pipe.
Step S3: roll state steel heat treatment
Roll state steel heat treatment and include quenching and tempering.This steel grade Ac1 temperature is 706 DEG C, and Ac3 temperature is 863 DEG C, and the temperature of quenching is higher than Ac3 temperature 30～70 DEG C, the Quench heating time is commonly used empirical equation т=a × K × D and calculates, in formula, т is heat time heating time, and a is heating coefficient, and heat treatment on spot stove heating coefficient is 3, K is shove charge correction factor, value is 4.2, and D is sample effective thickness, and the effective thickness after roll seamless steel tube is generally 5.5mm, therefore hardening heat is 920 ± 10 DEG C, is incubated 65～70 minutes at 920 ± 10 DEG C；Temperature is less than Ar1 temperature, tests room optimization of Heat Treatment Process by room, finally determines that the temperature of tempering is 680 ± 10 DEG C, and tempering is about the Quench heating time 1.2 times, therefore 680 ± 10 DEG C of tempering insulations 70～80 minutes heat time heating time.This Technology for Heating Processing ensure that the lumber recovery of seamless steel pipe.
Through the anti-H of high-intensity high-tenacity that said process produces2The weight/mass percentage composition of S corrosion tubing material chemical composition is: C 0.158%～0.167%, Si 0.298%～0.322%, Mn 0.499%～0.514%, Cr 0.98%～1.12%, Mo 0.377%～0.405%, P≤0.018%, S≤0.01%, V 0.051%～0.054%, Ti 0.011%～0.017%, Al 0.016%～0.021%, remaining is Fe, and mass fraction amounts to 100%.
The chemical composition of each embodiment is detected, the anti-H of high-intensity high-tenacity of each embodiment2The weight/mass percentage composition of S corrosion tubing material chemical composition is as shown in table 1.Harmful element and the content of gas in each embodiment are as shown in table 2.
By the strict control of the content to brittle crystal boundary element S, P and harmful element As, Sn, Pb, Sb and Bi, ensure the mechanical property that oil pipe is good.By controlling C and Mn chemical composition in steel, improve the corrosion resistance of steel.Strengthen resistance to corrosion by adding the Cr of certain content, improve steel grade quenching degree.Quenching degree and thermostrength is improved by adding Mo.Ti is strong deoxidizer in steel, and it can make the dense internal organization of steel, crystal grain thinning, thus improve the mechanical property of steel.V can thinning microstructure crystal grain, improve intensity and toughness.Al can crystal grain thinning, improve impact flexibility, Al also has non-oxidizability and corrosion resistance, Al with Cr, Si share, and is remarkably improved high temperature non-scale performance and the ability of high-temperature corrosion resistance of steel.
The anti-H of high-intensity high-tenacity to each embodiment2The metallographic structure of S corrosion oil pipe detects, and tests mechanical property, and result is the most as shown in Table 3 and Table 4.
Table 1 each embodiment composition (mass percent/%)
| Embodiment | C | Si | Mn | P | S | Cr | Mo | V | Ti | Al |
| Embodiment 1 | 0.164 | 0.317 | 0.514 | 0.018 | 0.010 | 1.12 | 0.398 | 0.051 | 0.011 | 0.021 |
| Embodiment 2 | 0.160 | 0.322 | 0.504 | 0.015 | 0.008 | 1.02 | 0.386 | 0.054 | 0.015 | 0.020 |
| Embodiment 3 | 0.158 | 0.305 | 0.501 | 0.012 | 0.009 | 0.98 | 0.377 | 0.052 | 0.017 | 0.019 |
| Embodiment 4 | 0.167 | 0.298 | 0.499 | 0.017 | 0.008 | 1.10 | 0.405 | 0.053 | 0.014 | 0.016 |
Table 2 each embodiment five-harmful elements and gas content (ppm)
| Embodiment | As | Sn | Sb | Bi | Pb | H | O | N |
| Embodiment 1 | 31 | 30 | 2.1 | 0.1 | 18 | 0.2 | 18 | 79 |
| Embodiment 2 | 19 | 31 | 3.5 | 0.2 | 15 | 1.2 | 26 | 68 |
| Embodiment 3 | 33 | 28 | 3.7 | 0.3 | 20 | 0.9 | 27 | 43 |
| Embodiment 4 | 30 | 29 | 1.6 | 0.1 | 17 | 1.1 | 21 | 57 |
| Desired value | ≤100 | ≤100 | ≤50 | ≤50 | ≤50 | ≤2.5 | ≤30 | ≤80 |
The metallographic structure testing result of each embodiment of table 3
The mechanical experimental results of each embodiment of table 4
As can be found from Table 3, each example field trash is tiny, be evenly distributed, and organizational structure is suitable, and crystal grain is ultra-fine grain, and grain size can reach 10 grades.From table 4, it can be seen that each embodiment has good strength, higher toughness, the seamless steel pipe prepared with it, there is good high epistasis and high tenacity.
The anti-H of high-intensity high-tenacity to the present invention2S corrodes its anti-H of coiled tubing test2The performance of S corrosion.According to the NACE solution of National Association of Corrosion Engineers's NACE Standard TM 0177-2005 standard recommendation, cleaned sample is placed in the corrosion container of injection experiments liquid and sealing, carefully loads after logical inert gas purge experiment container, be passed through H2S gas is the most saturated to it, the record experiment time started, within continuous 720 hours, soaks through NACE solution, checks under amplifying 10 times whether sample ruptures or have destructive crackle.Test result indicate that, the stretching of experience 720h permanent load, sample all remains intact, and corrosion cracking phenomenon does not occurs, and the anti-H of material is described2The ability of S stress corrosion cracking reaches standard-required.
The composition design and the preparation method that use the present invention are prepared 1 ton of steel and can be created economic benefit more than 300 yuan, optimize product structure, improve product specification, fill up at anti-H2The blank of S corrosion field.
Claims (4)
1. the anti-H of high-intensity high-tenacity2The preparation method of S corrosion oil pipe, it is characterised in that including: STEELMAKING PRODUCTION, the rolling of steel and roll state steel heat treatment, described STEELMAKING PRODUCTION includes: molten iron pretreatment, converter smelting, LF refine, VD vacuum outgas and round billet continuous casting；Described converter smelting uses desulphurised hot metal to smelt, every stove molten iron is 100 tons, every stove molten iron adds ferrosilicon 350kg, ferromanganese 850kg, ferrochrome 2000kg, molybdenum-iron 880kg, vanadium iron 100kg, ferrotianium 50kg, the weight/mass percentage composition of the composition of the molten iron of the terminal of described converter smelting includes: C >=0.06%, P≤0.015%, described converter smelting uses single slag technique to smelt, and before tapping, every stove molten iron adds 200kg white lime slag making, finishing slag basicity >=3.0；Described LF refine carries out slag making desulfurization, composition adjustment and warming temperature according to molten steel composition and the temperature of converter smelting, and slag former is CaO-CaF2Molten steel per ton adds 8-10kg slag former, adjust molten steel composition by following weight/mass percentage composition to include: C 0.16%, Si 0.30%, Mn 0.50%, Cr 1.0%, Mo 0.40%, P≤0.018%, S≤0.01%, V 0.052%, Ti 0.015%, Al 0.02%, the target temperature of warming temperature is 1536 DEG C；Vacuum≤the 0.06kPa of described VD vacuum outgas, deep vacuum time >=13min, soft blow Ar >=10min；The constant pulling rate of described round billet continuous casting is 1m/min, molten steel overheat Δ T≤30 DEG C；The described state steel heat treatment that rolls includes quenching and tempering, and the temperature of described quenching is 920 ± 10 DEG C, is incubated 65～70 minutes at 920 ± 10 DEG C；The temperature of described tempering is 680 ± 10 DEG C, is incubated 70～80 minutes at 680 ± 10 DEG C；The anti-H of high-intensity high-tenacity prepared2The weight/mass percentage composition of the material chemical composition of S corrosion oil pipe includes: C 0.158%～0.167%, Si 0.298%～0.322%, Mn 0.499%～0.514%, Cr 0.98%～1.12%, Mo 0.377%～0.405%, P≤0.018%, S≤0.01%, V 0.051%～0.054%, Ti 0.011%～0.017%, Al 0.016%～0.021%, remaining is Fe, and mass fraction amounts to 100%.
2. the anti-H of high-intensity high-tenacity as claimed in claim 12The preparation method of S corrosion oil pipe, it is characterised in that the rolling of described steel specifically includes that the heating of round base, perforation, tube rolling and stretch reducing.
3. the anti-H of high-intensity high-tenacity as claimed in claim 22The preparation method of S corrosion oil pipe, it is characterised in that: the temperature of described round base heating is 1250～1270 DEG C, and the temperature of described perforation is 1180～1250 DEG C, and the temperature of described tube rolling is 1020～1150 DEG C, and the temperature of described stretch reducing is 750～820 DEG C.
4. the anti-H of high-intensity high-tenacity as described in any one of claims 1 to 32The preparation method of S corrosion oil pipe, it is characterised in that the anti-H of described high-intensity high-tenacity prepared2The weight/mass percentage composition of the material chemical composition of S corrosion oil pipe includes: C 0.164%, Si 0.317%, Mn 0.514%, Cr 1.12%, Mo 0.398%, P 0.018%, S 0.010%, V 0.051%, Ti 0.011% and Al 0.021%；Or, C 0.160%, Si 0.322%, Mn 0.504%, Cr 1.02%, Mo 0.386%, P 0.015%, S 0.008%, V 0.054%, Ti 0.015% and Al 0.020%；Or, C 0.158%, Si 0.305%, Mn 0.501%, Cr 0.98%, Mo 0.377%, P 0.012%, S 0.009%, V 0.052%, Ti 0.017% and Al 0.019%；Or, C 0.167%, Si 0.298%, Mn 0.499%, Cr 1.10%, Mo 0.405%, P 0.017%, S 0.008%, V 0.053%, Ti 0.014% and Al 0.016%.
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| JPS634047A (en) * | 1986-06-20 | 1988-01-09 | Sumitomo Metal Ind Ltd | High-tensile steel for oil well excellent in sulfide cracking resistance |
| CN103361558A (en) * | 2013-05-09 | 2013-10-23 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing wet-H2S-corrosion-resistant T95 steel-grade oil well pipe and production method thereof |
| CN103436787A (en) * | 2013-08-23 | 2013-12-11 | 内蒙古包钢钢联股份有限公司 | Low-cost rare earth-containing anti-H2S corrosion petroleum casing pipe material and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS634047A (en) * | 1986-06-20 | 1988-01-09 | Sumitomo Metal Ind Ltd | High-tensile steel for oil well excellent in sulfide cracking resistance |
| CN103361558A (en) * | 2013-05-09 | 2013-10-23 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing wet-H2S-corrosion-resistant T95 steel-grade oil well pipe and production method thereof |
| CN103436787A (en) * | 2013-08-23 | 2013-12-11 | 内蒙古包钢钢联股份有限公司 | Low-cost rare earth-containing anti-H2S corrosion petroleum casing pipe material and production method thereof |
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