CN103820714B

CN103820714B - The anti-CO of high-intensity high-tenacity2the preparation method of corrosion sleeve pipe

Info

Publication number: CN103820714B
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: Inner Mongolia Baotou Steel Union Co Ltd
Current assignee: Inner Mongolia Baotou Steel Union Co Ltd
Priority date: 2014-02-21
Filing date: 2014-02-21
Publication date: 2016-09-07
Anticipated expiration: 2034-02-21
Also published as: CN103820714A

Abstract

The invention discloses a kind of anti-CO of high-intensity high-tenacity₂The preparation method of corrosion sleeve pipe, including: STEELMAKING PRODUCTION, the rolling of steel and roll state steel heat treatment.The chemical composition of the material of the present invention is rationally, employing crystal grain refines and refined crystalline strengthening technology makes the anti-CO of high-intensity high-tenacity₂Corrosion sleeve pipe has higher anti-CO₂Corrosive nature.

Description

The anti-CO of high-intensity high-tenacity2The preparation method of corrosion sleeve pipe

Technical field

The present invention relates to metal material field, specifically, relate to a kind of anti-CO of high-intensity high-tenacity₂The system of corrosion sleeve pipe Preparation Method.

Background technology

CO during petroleum gas drilling, in stratum₂The equipment such as oil pipe, sleeve pipe and pipeline can be caused serious corruption Erosion, shows according to related data, CO₂Corrosion is one of key factor threatening oil gas field safety in production.The Ekofisk of external Norway Oil field, Spruce from Northern Germany Region of Oil-gas field, the U.S. and more Canadian oil gas fields, Middle East oil gas field, Southeast Asia offshore oilfield etc. All there is CO₂Etching problem.Oil field, China land or marine oil field all occurred due to CO₂The oil well that corrosion causes stops Produce, scrap accident, economic loss and personal security all by serious threat.China Tarim Basin, long celebrating, Sichuan, North China, river at present All there is serious CO in Han Deng main force oil field₂Corrosion.The nineties in last century, the state such as the most Japanese, Argentinian has developed into this type of Product, 2000 Nian Hou China Baosteels, Steel Tube in Tianjin group successively develop this series products, and product is many based on 9Cr, 13Cr, so And it is known that 9Cr, 13Cr alloy content is higher so that its cost is higher, in the oil field that some are the barrenst, uses 9Cr, 13Cr carbon dioxide corrosion-resistant, it appears particularly luxurious and waste, therefore, exploiting economy type resistant to carbon dioxide tubing and casing, become For industry much-talked-about topic.As domestic emphasis steel and iron industry base, develop anti-CO₂Corrosion sleeve pipe, can not only be at rust-proof oil Certain market is striven in sleeve pipe field, while creating economic benefit for enterprise, optimizes the product structure that Baogang is current, promotes Baogang seamless pipe product specification.

Summary of the invention

The technical problem to be solved is to provide a kind of anti-CO of high-intensity high-tenacity₂The preparation side of corrosion sleeve pipe Method, can prepare the anti-CO of high-intensity high-tenacity with good corrosion resistance₂Corrosion sleeve pipe.

Technical scheme is as follows:

A kind of anti-CO of high-intensity high-tenacity₂The preparation method of corrosion sleeve pipe, including: STEELMAKING PRODUCTION, the rolling of steel and roll state Steel heat treatment, the anti-CO of high-intensity high-tenacity prepared₂The weight/mass percentage composition of the material chemical composition of corrosion sleeve pipe includes: C 0.159%～0.166%, Si 0.241%～0.248%, Mn0.427%～0.574%, Cr 2.92%～3.1%, Mo 0.373%～0.417%, P≤0.015%, S≤0.011%, V 0.05%～0.052%, Ti 0.013%～0.18%, Al 0.018%～0.022%, 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 circle base are even Casting.

Further, described converter smelting uses 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 terminal of described converter smelting The weight/mass percentage composition of the composition of molten iron includes: C >=0.06%, P≤0.015%；Described converter smelting uses single slag technique smelting Refining, before tapping, every stove molten iron adds 200kg white lime slag making, finishing slag basicity >=3.0；Described LF refine is according to the molten steel of converter smelting Composition and temperature carry out slag making desulfurization, composition adjustment and warming temperature, and slag former is CaO-CaF₂, molten steel per ton adds 8-10kg Slag former, adjusts molten steel composition by following weight/mass percentage composition and includes: C 0.16%, Si 0.245%, Mn0.45%, Cr 3.0%, Mo 0.40%, P≤0.015%, S≤0.011%, V 0.051%, Ti 0.015%, Al 0.02%, warming temperature Target temperature be 1540 DEG C；Vacuum≤the 0.06KPa of described VD vacuum outgas, deep vacuum time >=13min, soft blow Ar >= 10 minutes；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: described round base heating temperature be 1280 DEG C, the temperature of described perforation is 1200～1250 DEG C, described in roll The temperature of pipe is 1100～1180 DEG C, and the temperature of described stretch reducing is 780～850 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 are incubated 70～80 minutes；The temperature of described tempering is 680 ± 10 DEG C, is incubated 90～100 minutes at 680 ± 10 DEG C.

Further, the anti-CO of described high-intensity high-tenacity prepared₂The quality hundred of the material chemical composition of corrosion sleeve pipe Content is divided to include: C 0.166%, Si 0.247%, Mn 0.505%, Cr 2.95%, Mo0.392%, P 0.015%, S 0.011%, V 0.051%, Ti 0.018% and Al 0.020%；Or, C0.165%, Si 0.242%, Mn 0.574%, Cr 2.92%, Mo 0.377%, P 0.013%, S 0.009%, V 0.052%, Ti 0.017% and Al 0.022%；Or Person, C 0.159%, Si 0.241%, Mn 0.551%, Cr 2.98%, Mo 0.373%, P 0.012%, S 0.008%, V 0.052%, Ti 0.013% and Al0.018%；Or, C 0.161%, Si 0.248%, Mn 0.427%, Cr 3.10%, Mo 0.417%, P 0.011%, S 0.007%, V 0.050%, Ti 0.014% and Al 0.018%.

The technique effect of the present invention is as follows:

1, the anti-CO of the high-intensity high-tenacity of the present invention₂The chemical composition of the material of corrosion sleeve pipe rationally makes high intensity and high ductility The anti-CO of property₂Corrosion sleeve pipe has higher anti-CO₂Corrosive nature.

2, the present invention uses crystal grain refinement to make material have high intensity and high tenacity, rational smelting with refined crystalline strengthening technology Refining continuous casting process, rolling mill practice, Technology for Heating Processing make product have relatively high yield.

3, the anti-CO of high-intensity high-tenacity that the preparation method that the present invention provides obtains₂The quality of corrosion sleeve pipe is good, produces Efficiency is high, low cost, and anticorrosive so that material energy-saving environmental protection, low chromium content makes material good in economic efficiency, is suitable for extensive Produce, there is good marketing using value.

Detailed description of the invention

From the market demand, economic benefit and social benefit, the present invention is by the effect design in the material of each element Rational chemical composition, by smelting continuous casting, drilling/rolling, hardening and tempering process are produced intensity and are up to 110psi grade of steel, impact Toughness is significantly larger than API 5CT standard-required, and the anti-CO of high-intensity high-tenacity that corrosion resistance is good₂Corrosion sleeve pipe.This The anti-CO of bright high-intensity high-tenacity₂Specifically comprising the following steps that of the preparation method of corrosion sleeve pipe

Step S1: STEELMAKING PRODUCTION

STEELMAKING PRODUCTION includes: molten iron pretreatment, converter smelting, LF refine, VD vacuum outgas and round billet continuous casting.STEELMAKING PRODUCTION 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.

Converter smelting uses desulphurised hot metal, for non-metallic inclusion, ferrosilicon, ferromanganese, ferrochrome, molybdenum-iron, vanadium in suppression material Ferrum and ferro-titanium necessary deoxidation alloying before addition, addition is according to alloy content, steel in its recovery rate, ferrous alloy In material, composition design content requirement calculates.Every stove molten iron is 100 tons, and the every stove of ferrosilicon adds 350kg, the every stove of ferromanganese adds The every stove of 900kg, ferrochrome adds 6500kg, the every stove of molybdenum-iron adds 800kg, the every stove of vanadium iron adds 100kg, the every stove of ferrotianium adds 50kg.Owing to gas content such as oxygen nitrogen can be made in material while carburetting to increase, the therefore composition of the molten iron of converter terminal The control target of weight/mass percentage composition includes: C >=0.06%, P≤0.015%.Single slag technique is used to smelt, every stove ferrum before tapping Water 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 failure Must skim.

In LF refine link, carry out slag making desulfurization, composition adjustment and warming temperature according to converter molten steel composition and temperature. Slag former is CaO-CaF₂, molten steel per ton adds 8-10kg slag former, adjusts the mesh of molten steel composition by following weight/mass percentage composition Scale value includes: C 0.16%, Si 0.245%, Mn 0.45%, Cr 3.0%, Mo 0.40%, P≤0.015%, S≤ 0.011%, V 0.051%, Ti 0.015%, Al 0.02%, the target temperature of warming temperature is 1540 DEG C.

The deep vacuum desired value≤0.06KPa of VD vacuum outgas, deep vacuum time >=13 minute, soft blow Ar >=10 point Clock, 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 ℃.During cooling, way of stacking can be used summer to cool down, air port should be avoided simultaneously；Burial pit can be used winter slow Cooling.

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.Should With the seamless steel pipe that Ф 180MPM unit rolling specs is Φ 177.8mm × 9.19mm, formulate according to laboratory thermal simulation experiment Rolling mill practice, rolling mill practice is: circle base is heated uniformly to 1280 DEG C in rotary heating furnace；Circle base perforation temperature be 1200～ 1250℃；In this temperature range, tensile strength is relatively low, and elongation percentage is higher, and the temperature drop bored a hole from heating furnace ejection to perforating machine It is about 50 DEG C；The temperature of tube rolling is 1100～1180 DEG C；The temperature of stretch reducing is 780～850 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.The temperature of quenching is selected by quenching degree experiment, and temperature is too high easily Causing original austenite grains to be grown up, temperature is too low, makes alloy diffusion incomplete, thus forming component segregation, by experiment Room contrast screening, the temperature of quenching is 920 ± 10 DEG C；Quenching Soaking Time is calculated by conventional empirical equation т=a × K × D, In formula, т is heat time heating time, and a is heating coefficient, and heat treatment on spot stove heating coefficient is 2.0, and K is shove charge correction factor, is worth and is 4.0, D is sample effective thickness, and the effective thickness of the steel pipe after rolling is generally 9.19mm, therefore Quenching Soaking Time be 70～ 80 minutes；Tempering insulation time is about 1.2 times of Quenching Soaking Time, and temperature controls, below steel grade Ac1 temperature, to pass through Technology for Heating Processing filters out optimum tempering temperature.Preferably Technology for Heating Processing be the temperature of quenching be 920 ± 10 DEG C, 920 ± 10 DEG C are incubated 70～80 minutes.The temperature of tempering is 680 ± 10 DEG C, is incubated 90～100 minutes at 680 ± 10 DEG C.

Through the anti-CO of high-intensity high-tenacity that said process produces₂The weight/mass percentage composition of corrosion shell material chemical composition For: C 0.159%～0.166%, Si 0.241%～0.248%, Mn 0.427%～0.574%, Cr 2.92%～ 3.1%, Mo 0.373%～0.417%, P≤0.015%, S≤0.011%, V 0.05%～0.052%, Ti 0.013% ～0.18%, Al 0.018%～0.022%, remaining is Fe, and mass fraction amounts to 100%.

The chemical composition of each example is detected, the anti-CO of high-intensity high-tenacity of each embodiment₂Corrosion shell material The weight/mass percentage composition studied point 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 sleeve pipe is good.The corrosion resistance of steel is improved by controlling C and Mn chemical composition in steel；Compared with prior art, C and the Mn content that the present invention is relatively low so that material has the most excellent corrosion resistance.Strengthen by adding the Cr of certain content Resistance to corrosion, improves steel grade quenching degree, and the Cr content of 2.92%～3.1% makes material have carbon dioxide corrosion-resistant performance While reduce cost.Quenching degree and thermostrength is improved by adding Mo.Ti is strong deoxidizer in steel, and it can make steel Dense internal organization, 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 can significantly carry The high temperature non-scale performance of Gao Gang and the ability of high-temperature corrosion resistance.

The anti-CO of high-intensity high-tenacity to each embodiment₂The metallographic structure of corrosion sleeve pipe detects, and to mechanical property Testing, 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	0.166	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

Table 2 each embodiment five-harmful elements 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
									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 embodiment field trash is tiny, be evenly distributed, and organizational structure is suitable, and grain size is original Austria Family name's body crystal grain, can reach 10 grades, belongs to ultra-fine grain, has obtained stable tempered sorbite after heat treatment.Can from table 4 Going out, each embodiment has good strength, higher toughness, and yield tensile ratio is less than 0.9, thus it is good to ensure that material in use has Good safety.The anti-CO of solution it is simulated in 10L high temperature and high pressure kettle₂Experiment, with compared with grade of steel plain C-Mn steel, resists CO₂Average corrosion rate is 2.5～3.5 times of plain C-Mn steel.The composition design and the preparation method that use the present invention prepare 1 ton Steel can create economic benefit more than 500 yuan, optimizes product structure, improves product specification.

Claims

1. the anti-CO of high-intensity high-tenacity₂The preparation method of corrosion sleeve pipe, it is characterised in that including: STEELMAKING PRODUCTION, the rolling of steel Making and roll state steel heat treatment, described STEELMAKING PRODUCTION includes: molten iron pretreatment, converter smelting, LF refine, VD vacuum outgas and circle base Continuous casting；Described converter smelting uses 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 composition of the molten iron of the terminal of described converter smelting Weight/mass percentage composition include: C >=0.06%, P≤0.015%, described converter smelting uses single slag technique to smelt, every before tapping Stove molten iron adds 200kg white lime slag making, finishing slag basicity >=3.0；Described LF refine is according to the molten steel composition of converter smelting and temperature Carrying out slag making desulfurization, composition adjustment and warming temperature, slag former is CaO-CaF₂, molten steel per ton adds 8-10kg slag former, presses Following weight/mass percentage composition adjusts molten steel composition and includes: C 0.16%, Si 0.245%, Mn 0.45%, Cr 3.0%, Mo 0.40%, P≤0.015%, S≤0.011%, V 0.051%, Ti 0.015%, Al 0.02%, the target temperature of warming temperature Degree is 1540 DEG C；Vacuum≤the 0.06KPa of described VD vacuum outgas, deep 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 DEG C；The rolling of described steel specifically includes that round base Heating, perforation, tube rolling and stretch reducing, the temperature of described round base heating is 1280 DEG C, the temperature of described perforation be 1200～ 1250 DEG C, the temperature of described tube rolling is 1100～1180 DEG C, and the temperature of described stretch reducing is 780～850 DEG C；Described roll state steel Heat treatment includes quenching and tempering, and tempering insulation time is 1.2 times of Quenching Soaking Time；The temperature of described quenching is 920 ± 10 DEG C, being incubated 70～80 minutes at 920 ± 10 DEG C, Quenching Soaking Time т=a × K × D, in formula, т is heat time heating time, heating system Number a is 2.0, and shove charge adjusted coefficient K is 4.0, and sample effective thickness D is 9.19mm；The temperature of described tempering is 680 ± 10 DEG C, It is incubated 90～100 minutes at 680 ± 10 DEG C；The anti-CO of high-intensity high-tenacity prepared₂The material chemical composition of corrosion sleeve pipe Weight/mass percentage composition include: C 0.159%～0.166%, Si 0.241%～0.248%, Mn 0.427%～ 0.574%, Cr 2.92%～3.1%, Mo 0.373%～0.417%, P≤0.015%, S≤0.011%, V 0.05%～ 0.052%, Ti 0.013%～0.18%, Al 0.018%～0.022%, remaining is Fe, and mass fraction amounts to 100%.

2. the anti-CO of high-intensity high-tenacity as claimed in claim 1₂The preparation method of corrosion sleeve pipe, it is characterised in that prepare The anti-CO of described high-intensity high-tenacity₂The weight/mass percentage composition of the material chemical composition of corrosion sleeve pipe includes: C 0.166%, Si 0.247%, Mn 0.505%, Cr 2.95%, Mo 0.392%, P 0.015%, S 0.011%, V 0.051%, Ti 0.018% and Al 0.020%；Or, C 0.165%, Si 0.242%, Mn 0.574%, Cr 2.92%, Mo 0.377%, P 0.013%, S 0.009%, V 0.052%, Ti 0.017% and Al 0.022%；Or, C 0.159%, Si 0.241%, Mn 0.551%, Cr 2.98%, Mo 0.373%, P 0.012%, S 0.008%, V 0.052%, Ti 0.013% and Al 0.018%；Or, C 0.161%, Si 0.248%, Mn 0.427%, Cr 3.10%, Mo 0.417%, P 0.011%, S 0.007%, V 0.050%, Ti 0.014% and Al 0.018%.