CN103820714A

CN103820714A - High-strength and high-toughness CO2 corrosion resistant bushing and making method thereof

Info

Publication number: CN103820714A
Application number: CN201410059792.XA
Authority: CN
Inventors: 刘金; 石晓霞; 马爱清; 王金龙; 张行刚; 寇莎莎
Original assignee: Baotou Iron and Steel Group Co Ltd
Current assignee: Baotou Iron and Steel Group Co Ltd; Inner Mongolia Baotou Steel Union Co Ltd
Priority date: 2014-02-21
Filing date: 2014-02-21
Publication date: 2014-05-28
Anticipated expiration: 2034-02-21
Also published as: CN103820714B

Abstract

The invention discloses a high-strength and high-toughness CO2 corrosion resistant bushing. The bushing comprises, by mass, 0.159-0.166% of C, 0.241-0.248% of Si, 0.427-0.574% of Mn, 2.92-3.1% of Cr, 0.373-0.417% of Mo, 0.015% or less of P, 0.011% or less of S, 0.05-0.052% of V, 0.013-0.18% of Ti, 0.018-0.022% of Al, and the balance Fe, and the sum of the mass fractions of the above components is 100%. The invention also discloses a making method of the high-strength and high-toughness CO2 corrosion resistant bushing. The method comprises the steps of steelmaking production, steel rolling and rolled steel heat treatment. The reasonability of the chemical components of the material of the bushing and the adoption of a crystal grain refinement and fine grain strengthening technology make the high-strength and high-toughness CO2 corrosion resistant bushing have a high CO2 corrosion resistance.

Description

The anti-CO of high-intensity high-tenacity 2corrosion sleeve pipe and preparation method thereof

Technical field

The present invention relates to metal material field, specifically, relate to the anti-CO of a kind of high-intensity high-tenacity ₂corrosion sleeve pipe and preparation method thereof.

Background technology

In oil and gas drilling process, the CO in stratum ₂can cause heavy corrosion to equipment such as oil pipe, sleeve pipe and pipelines, show CO according to related data ₂corrosion is to threaten one of important factor of oil-gas field safety in production.All there is CO in Ekofisk oil field, Spruce from Northern Germany Region of Oil-gas field, the U.S. and more Canadian oil-gas fields of Norway, Middle East oil-gas field, South East Asia offshore oilfield etc. abroad ₂etching problem.Oil field, China land or marine oil field all occurred due to CO ₂the oil well that corrosion causes stops production, scraps accident, and financial loss and personal security are all subject to serious threat.All there is serious CO in the main force oil fields such as current China Tarim Basin, long celebrating, Sichuan, North China, Jiang-Han Area ₂corrosion.The nineties in last century, the external state such as Japanese, Argentinian has been developed to this series products, and 2000 Nian Hou China Baosteels, Steel Tube in Tianjin group priority have been developed this series products, product is main mainly with 9Cr, 13Cr, but well-known, 9Cr, 13Cr alloy content are higher, make its cost higher, in some comparatively barren oil fields, adopt 9Cr, 13Cr carbon dioxide corrosion-resistant, seem particularly luxurious and waste, therefore, exploiting economy type resistant to carbon dioxide tubing and casing, becomes industry much-talked-about topic.As domestic emphasis Iron And Steel Industry base, develop anti-CO ₂corrosion sleeve pipe, can not only strive for certain market in rust-proof oil sleeve pipe field, when creating economic benefit, has optimized the current product structure of Baogang for enterprise, has promoted Baogang's seamless tube product specification.

Summary of the invention

Technical problem to be solved by this invention is to provide the anti-CO of a kind of high-intensity high-tenacity ₂corrosion sleeve pipe, has good corrosion resistance.

Technical scheme of the present invention is as follows:

The anti-CO of a kind of high-intensity high-tenacity ₂corrosion sleeve pipe, the quality percentage composition of its material chemical composition comprises: C0.159%～0.166%, Si0.241%～0.248%, Mn0.427%～0.574%, Cr2.92%～3.1%, Mo0.373%～0.417%, P≤0.015%, S≤0.011%, V0.05%～0.052%, Ti0.013%～0.18%, Al0.018%～0.022%, all the other are Fe, and massfraction amounts to 100%.

Further, the anti-CO of described high-intensity high-tenacity ₂the quality percentage composition of the chemical composition of corrosion sleeve pipe comprises: C0.166%, Si0.247%, Mn0.505%, Cr2.95%, Mo0.392%, P0.015%, S0.011%, V0.051%, Ti0.018% and Al0.020%; Or, C0.165%, Si0.242%, Mn0.574%, Cr2.92%, Mo0.377%, P0.013%, S0.009%, V0.052%, Ti0.017% and Al0.022%; Or, C0.159%, Si0.241%, Mn0.551%, Cr2.98%, Mo0.373%, P0.012%, S0.008%, V0.052%, Ti0.013% and Al0.018%; Or, C0.161%, Si0.248%, Mn0.427%, Cr3.10%, Mo0.417%, P0.011%, S0.007%, V0.050%, Ti0.014% and Al0.018%.

Another technical problem to be solved by this invention is to provide the anti-CO of a kind of high-intensity high-tenacity ₂the preparation method of corrosion sleeve pipe, can prepare the anti-CO of high-intensity high-tenacity with good corrosion resistance ₂corrosion sleeve pipe.

Another technical scheme of the present invention is as follows:

The anti-CO of a kind of high-intensity high-tenacity ₂the preparation method of corrosion sleeve pipe, comprising: the rolling of STEELMAKING PRODUCTION, steel and roll the thermal treatment of state steel, the anti-CO of high-intensity high-tenacity preparing ₂the quality percentage composition of the material chemical composition of corrosion sleeve pipe comprises: C0.159%～0.166%, Si0.241%～0.248%, Mn0.427%～0.574%, Cr2.92%～3.1%, Mo0.373%～0.417%, P≤0.015%, S≤0.011%, V0.05%～0.052%, Ti0.013%～0.18%, Al0.018%～0.022%, all the other are Fe, and massfraction amounts to 100%.

Further, described STEELMAKING PRODUCTION comprises: hot metal pretreatment, converter smelting, LF refining, VD vacuum outgas and round billet continuous casting.

Further, described converter smelting adopts desulphurised hot metal to smelt, and every stove molten iron is 100 tons, and every stove molten iron adds ferrosilicon 350kg, ferromanganese 900kg, ferrochrome 6500kg, molybdenum-iron 800kg, vanadium iron 100kg, ferrotianium 50kg; The quality percentage composition of the composition of the molten iron of the terminal of described converter smelting comprises: C>=0.06%, P≤0.015%; Described converter smelting adopts single slag technique to smelt, and before tapping, every stove molten iron adds the slag making of 200kg lime, finishing slag basicity>=3.0; Described LF refining is carried out slag making desulfurization, composition adjustment and warming temperature according to the molten steel composition of converter smelting and temperature, and slag former is CaO-CaF ₂molten steel per ton adds 8-10kg slag former, adjusting molten steel composition by following quality percentage composition comprises: C0.16%, Si0.245%, Mn0.45%, Cr3.0%, Mo0.40%, P≤0.015%, S≤0.011%, V0.051%, Ti0.015%, Al0.02%, and the target temperature of warming temperature is 1540 ℃; Vacuum tightness≤the 0.06KPa of described VD vacuum outgas, dark vacuum time>=13min, soft blow Ar>=10 minute; The constant pulling rate of described round billet continuous casting is 1m/min, molten steel overheat Δ T≤30 ℃.

Further, the rolling of described steel mainly comprises: the heating of circle base, perforation, tube rolling and tension reducing.

Further: the temperature of described round base heating is 1280 ℃, and the temperature of described perforation is 1200～1250 ℃, and the temperature of described tube rolling is 1100～1180 ℃, and the temperature of described tension reducing is 780～850 ℃.

Further: described in roll the thermal treatment of state steel comprise quench and tempering, the temperature of described quenching is 920 ± 10 ℃, 920 ± 10 ℃ insulation 70～80 minutes; The temperature of described tempering was 680 ± 10 ℃, 680 ± 10 ℃ of insulations 90～100 minutes.

Further, the anti-CO of described high-intensity high-tenacity preparing ₂the quality percentage composition of the material chemical composition of corrosion sleeve pipe comprises: C0.166%, Si0.247%, Mn0.505%, Cr2.95%, Mo0.392%, P0.015%, S0.011%, V0.051%, Ti0.018% and Al0.020%; Or, C0.165%, Si0.242%, Mn0.574%, Cr2.92%, Mo0.377%, P0.013%, S0.009%, V0.052%, Ti0.017% and Al0.022%; Or, C0.159%, Si0.241%, Mn0.551%, Cr2.98%, Mo0.373%, P0.012%, S0.008%, V0.052%, Ti0.013% and Al0.018%; Or, C0.161%, Si0.248%, Mn0.427%, Cr3.10%, Mo0.417%, P0.011%, S0.007%, V0.050%, Ti0.014% and Al0.018%.

Technique effect of the present invention is as follows:

1, the anti-CO of high-intensity high-tenacity of the present invention ₂the chemical composition of the material of corrosion sleeve pipe rationally makes the anti-CO of high-intensity high-tenacity ₂corrosion sleeve pipe has higher anti-CO ₂corrosive nature.

2, the present invention adopts grain refining and refined crystalline strengthening technology to make material have high strength and high tenacity, reasonably smelts continuous casting process, rolling technology, thermal treatment process product is had compared with high yield.

3, the anti-CO of high-intensity high-tenacity that preparation method provided by the invention obtains ₂the quality of corrosion sleeve pipe is good, and production efficiency is high, cost is low, anticorrosive, makes material energy-saving environmental protection, and low chromium content makes material good in economic efficiency, is suitable for scale operation, has good marketing using value.

Embodiment

From the market requirement, economic benefit and social benefit, by each element, the effect in material has designed rational chemical composition in the present invention, produce intensity up to 110psi grade of steel by smelting continuous casting, drilling/rolling, hardening and tempering process, impelling strength is far away higher than API5CT standard-required, and the good anti-CO of high-intensity high-tenacity of corrosion resistance ₂corrosion sleeve pipe.The anti-CO of high-intensity high-tenacity of the present invention ₂the preparation method's of corrosion sleeve pipe concrete steps are as follows:

Step S1: STEELMAKING PRODUCTION

STEELMAKING PRODUCTION comprises: hot metal pretreatment, converter smelting, LF refining, VD vacuum outgas and round billet continuous casting.Steelmaking process adopts fixed nitrogen technology, deoxy technology, Clean Steel technology to make blank have good quality.

By hot metal pretreatment, molten iron is carried out to pre-desulfurization.

Converter smelting adopts desulphurised hot metal, for suppressing non-metallic inclusion in material, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron, vanadium iron and ferro-titanium be necessary deoxidation alloying before adding, and add-on calculates according to Composition Design content requirement in its recovery rate, ferrous alloy interalloy content, steel.Every stove molten iron is 100 tons, and the every stove of ferrosilicon adds 350kg, the every stove of ferromanganese to add 900kg, the every stove of ferrochrome to add 6500kg, the every stove of molybdenum-iron to add 800kg, the every stove of vanadium iron to add 100kg, the every stove of ferrotianium to add 50kg.Due to carburetting time, can make in material gas content increase as oxygen nitrogen, therefore the control target of the quality percentage composition of the composition of the molten iron of converter terminal comprises: C >=0.06%, P≤0.015%.Adopt single slag technique to smelt, before tapping, every stove molten iron adds the slag making of 200kg lime, finishing slag basicity >=3.0.For guaranteeing the cleanliness factor of material, necessary pushing off the slag when tapping, pushing off the slag unsuccessfully must be skimmed.

In LF refining link, carry out slag making desulfurization, composition adjustment and warming temperature according to converter molten steel composition and temperature.Slag former is CaO-CaF ₂molten steel per ton adds 8-10kg slag former, the target value of adjusting molten steel composition by following quality percentage composition comprises: C0.16%, Si0.245%, Mn0.45%, Cr3.0%, Mo0.40%, P≤0.015%, S≤0.011%, V0.051%, Ti0.015%, Al0.02%, the target temperature of warming temperature is 1540 ℃.

The dark vacuum tightness target value≤0.06KPa of VD vacuum outgas, dark vacuum time >=13 minute, soft blow Ar >=10 minute, to guarantee gas content lower in material.

Round billet continuous casting process adopts induction stirring technique, and constant pulling rate is controlled at 1m/min, molten steel overheat Δ T≤30 ℃.When cooling, it is cooling that can adopt way of stacking to carry out summer, should avoid air port simultaneously; Can adopt burial pit Slow cooling winter.

Step S2: the rolling of steel

The rolling of steel mainly comprises: the heating of circle base, perforation, tube rolling and tension reducing, detailed process is: circle base → sawing → circle base heating → perforation → tube rolling → tension reducing → cooling → crop end → align → check → pack → weigh → warehouse-in.Application Ф 180MPM unit rolling specs is the weldless steel tube of Φ 177.8mm × 9.19mm, formulates rolling technology according to laboratory thermal simulation experiment, and rolling technology is: circle base homogeneous heating to 1280 ℃ in rotary heating furnace; The temperature of circle base perforation is 1200～1250 ℃; In this temperature range, tensile strength is lower, and unit elongation is higher, and the temperature drop of perforation is about 50 ℃ from process furnace ejection to tapping machine; The temperature of tube rolling is 1100～1180 ℃; The temperature of tension reducing is 780～850 ℃.This rolling technology has guaranteed the lumber recovery of weldless steel tube.

Step S3: roll the thermal treatment of state steel

Roll the thermal treatment of state steel and comprise quenching and tempering.The temperature of quenching is tested selected by hardening capacity, excess Temperature easily causes original austenite grains to be grown up, and temperature is too low makes alloy diffusion incomplete, thus forming component segregation, chamber contrast screening by experiment, the temperature of quenching is 920 ± 10 ℃; Quenching Soaking Time is calculated by conventional experimental formula т=a × K × D, in formula, т is heat-up time, a is heating coefficient, on-the-spot heat treatment furnace heating coefficient is 2.0, K is shove charge correction factor, and value is that 4.0, D is sample net thickness, the net thickness of the steel pipe after rolling is generally 9.19mm, and therefore Quenching Soaking Time is 70～80 minutes; Tempering insulation time is about 1.2 times of Quenching Soaking Time, and tempering temperature is controlled at below steel grade Ac1 temperature, filters out optimum tempering temperature by thermal treatment process.Preferred thermal treatment process was that the temperature of quenching is 920 ± 10 ℃, 920 ± 10 ℃ of insulations 70～80 minutes.The temperature of tempering was 680 ± 10 ℃, 680 ± 10 ℃ of insulations 90～100 minutes.

The anti-CO of high-intensity high-tenacity producing through said process ₂the quality percentage composition of corrosion shell material chemical composition is: C0.159%～0.166%, Si0.241%～0.248%, Mn0.427%～0.574%, Cr2.92%～3.1%, Mo0.373%～0.417%, P≤0.015%, S≤0.011%, V0.05%～0.052%, Ti0.013%～0.18%, Al0.018%～0.022%, all the other are Fe, and massfraction amounts to 100%.

Chemical composition to each example detects, the anti-CO of high-intensity high-tenacity of each embodiment ₂the quality percentage composition of corrosion shell material chemical composition is as shown in table 1.Harmful element in each embodiment and the content of gas are as shown in table 2.

By the strict control of the content to embrittlement crystal boundary element S, P and harmful element As, Sn, Pb, Sb and Bi, guarantee the mechanical property that sleeve pipe is good.Improve the solidity to corrosion of steel by C and Mn chemical composition in control steel; Compared with prior art, the C that the present invention is lower and Mn content, make material have more good erosion resistance.Strengthen resistance to corrosion by the Cr that adds certain content, improve steel grade hardening capacity, the cost reducing by when 2.92%～3.1% Cr content makes material have carbon dioxide corrosion-resistant performance.By adding Mo to improve hardening capacity and thermostrength.Ti is strong reductor 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, improves intensity and toughness.Al can crystal grain thinning, improves impelling strength, and Al also has oxidation-resistance and corrosion resistance, and Al and Cr, Si share, and can significantly improve the high temperature non-scale performance of steel and the ability of high-temperature corrosion resistance.

To the anti-CO of the high-intensity high-tenacity of each embodiment ₂the metallographic structure of corrosion sleeve pipe detects, and mechanical property is tested, and result respectively as shown in Table 3 and Table 4.

The each embodiment composition of table 1 (mass percent/%)

Embodiment	C	Si	Mn	P	S	Cr	Mo	V	Ti	Al
											Embodiment 1	0.166	0.247	0.505	0.015	0.011	2.95	0.392	0.051	0.018	0.020
Embodiment 2	0.165	0.242	0.574	0.013	0.009	2.92	0.377	0.052	0.017	0.022
											Embodiment 3	0.159	0.241	0.551	0.012	0.008	2.98	0.373	0.052	0.013	0.018
Embodiment 4	0.161	0.248	0.427	0.011	0.007	3.10	0.417	0.050	0.014	0.019

The each embodiment five-harmful elements of table 2 and gas content (ppm)

Embodiment	As	Sn	Sb	Bi	Pb	H	O	N
									Embodiment 1	30	16	5.0	0.6	23	1.1	18	66
Embodiment 2	27	18	9.0	0.6	28	1.1	21	68
									Embodiment 3	28	22	9.5	0.8	18	1.6	23	53
Embodiment 4	31	21	8.2	0.7	25	1.4	18	67
									Target value	≤100	≤100	≤50	≤50	≤50	≤2.5	≤30	≤80

The metallographic structure detected result of the each embodiment of table 3

The mechanical experimental results of the each embodiment of table 4

As can be found from Table 3, each embodiment inclusion is tiny, be evenly distributed, and weave construction is suitable, and grain fineness number is original austenite grains, can reach 10 grades, belongs to superfine crystal particle, has obtained stable tempered sorbite after thermal treatment.As can be seen from Table 4, each embodiment has good strength, higher toughness, and yield tensile ratio is less than 0.9, thereby guarantees that material in use has good security.In 10L high temperature and high pressure kettle, simulate the anti-CO of solution ₂experiment, compares with same grade of steel plain C-Mn steel, anti-CO ₂average corrosion rate is 2.5～3.5 times of plain C-Mn steel.Adopt Composition Design of the present invention and preparation method to prepare 1 ton of steel and can create economic benefit more than 500 yuan, optimized product structure, improved product specification.

Claims

1. the anti-CO of high-intensity high-tenacity ₂corrosion sleeve pipe, it is characterized in that, the quality percentage composition of its material chemical composition comprises: C0.159%～0.166%, Si0.241%～0.248%, Mn0.427%～0.574%, Cr2.92%～3.1%, Mo0.373%～0.417%, P≤0.015%, S≤0.011%, V0.05%～0.052%, Ti0.013%～0.18%, Al0.018%～0.022%, all the other are Fe, and massfraction amounts to 100%.

2. the anti-CO of high-intensity high-tenacity as claimed in claim 1 ₂corrosion sleeve pipe, is characterized in that, the quality percentage composition of its chemical composition comprises: C0.166%, Si0.247%, Mn0.505%, Cr2.95%, Mo0.392%, P0.015%, S0.011%, V0.051%, Ti0.018% and Al0.020%; Or, C0.165%, Si0.242%, Mn0.574%, Cr2.92%, Mo0.377%, P0.013%, S0.009%, V0.052%, Ti0.017% and Al0.022%; Or, C0.159%, Si0.241%, Mn0.551%, Cr2.98%, Mo0.373%, P0.012%, S0.008%, V0.052%, Ti0.013% and Al0.018%; Or, C0.161%, Si0.248%, Mn0.427%, Cr3.10%, Mo0.417%, P0.011%, S0.007%, V0.050%, Ti0.014% and Al0.018%.

3. the anti-CO of high-intensity high-tenacity ₂the preparation method of corrosion sleeve pipe, is characterized in that, comprising: the rolling of STEELMAKING PRODUCTION, steel and roll the thermal treatment of state steel, the anti-CO of high-intensity high-tenacity preparing ₂the quality percentage composition of the material chemical composition of corrosion sleeve pipe comprises: C0.159%～0.166%, Si0.241%～0.248%, Mn0.427%～0.574%, Cr2.92%～3.1%, Mo0.373%～0.417%, P≤0.015%, S≤0.011%, V0.05%～0.052%, Ti0.013%～0.18%, Al0.018%～0.022%, all the other are Fe, and massfraction amounts to 100%.

4. the anti-CO of high-intensity high-tenacity as claimed in claim 3 ₂the preparation method of corrosion sleeve pipe, is characterized in that, described STEELMAKING PRODUCTION comprises: hot metal pretreatment, converter smelting, LF refining, VD vacuum outgas and round billet continuous casting.

5. the anti-CO of high-intensity high-tenacity as claimed in claim 4 ₂the preparation method of corrosion sleeve pipe, is characterized in that,

Described converter smelting adopts desulphurised hot metal to smelt, every stove molten iron is 100 tons, every stove molten iron adds ferrosilicon 350kg, ferromanganese 900kg, ferrochrome 6500kg, molybdenum-iron 800kg, vanadium iron 100kg, ferrotianium 50kg, the quality percentage composition of the composition of the molten iron of the terminal of described converter smelting comprises: C >=0.06%, P≤0.015%, described converter smelting adopts single slag technique to smelt, and before tapping, every stove molten iron adds the slag making of 200kg lime, finishing slag basicity >=3.0;

Described LF refining is carried out slag making desulfurization, composition adjustment and warming temperature according to the molten steel composition of converter smelting and temperature, and slag former is CaO-CaF ₂molten steel per ton adds 8-10kg slag former, adjusting molten steel composition by following quality percentage composition comprises: C0.16%, Si0.245%, Mn0.45%, Cr3.0%, Mo0.40%, P≤0.015%, S≤0.011%, V0.051%, Ti0.015%, Al0.02%, and the target temperature of warming temperature is 1540 ℃;

Vacuum tightness≤the 0.06KPa of described VD vacuum outgas, dark vacuum time >=13min, soft blow Ar >=10 minute;

The constant pulling rate of described round billet continuous casting is 1m/min, molten steel overheat Δ T≤30 ℃.

6. the anti-CO of high-intensity high-tenacity as claimed in claim 3 ₂the preparation method of corrosion sleeve pipe, is characterized in that, the rolling of described steel mainly comprises: the heating of circle base, perforation, tube rolling and tension reducing.

7. the anti-CO of high-intensity high-tenacity as claimed in claim 6 ₂the preparation method of corrosion sleeve pipe, is characterized in that: the temperature of described round base heating is 1280 ℃, and the temperature of described perforation is 1200～1250 ℃, and the temperature of described tube rolling is 1100～1180 ℃, and the temperature of described tension reducing is 780～850 ℃.

8. the anti-CO of high-intensity high-tenacity as claimed in claim 3 ₂corrosion sleeve pipe preparation method, it is characterized in that: described in roll the thermal treatment of state steel comprise quench and tempering, the temperature of described quenching is 920 ± 10 ℃, 920 ± 10 ℃ insulation 70～80 minutes; The temperature of described tempering was 680 ± 10 ℃, 680 ± 10 ℃ of insulations 90～100 minutes.

9. the anti-CO of high-intensity high-tenacity as described in claim 3～8 any one ₂the preparation method of corrosion sleeve pipe, is characterized in that the anti-CO of described high-intensity high-tenacity preparing ₂the quality percentage composition of the material chemical composition of corrosion sleeve pipe comprises: C0.166%, Si0.247%, Mn0.505%, Cr2.95%, Mo0.392%, P0.015%, S0.011%, V0.051%, Ti0.018% and Al0.020%; Or, C0.165%, Si0.242%, Mn0.574%, Cr2.92%, Mo0.377%, P0.013%, S0.009%, V0.052%, Ti0.017% and Al0.022%; Or, C0.159%, Si0.241%, Mn0.551%, Cr2.98%, Mo0.373%, P0.012%, S0.008%, V0.052%, Ti0.013% and Al0.018%; Or, C0.161%, Si0.248%, Mn0.427%, Cr3.10%, Mo0.417%, P0.011%, S0.007%, V0.050%, Ti0.014% and Al0.018%.