CN101082109A - 110 steel grade carbon dioxide and chloride ion corrosion-proof oil well-pipe steel - Google Patents

Abstract

The 110 grade stainless steel resisting CO2 and chlorine ion corrosion for oil well pipe has the components including C 0.05-0.18 wt%, Si 0.2-1.00 wt%, Mn 0.20-1.00 wt%, Cr 10.0-14.0 wt%, Ni 0.5-3.0 wt%, Mo 0.1-0.5 wt%, Cu 0.5-1.5 wt%, V 0.03-0.08 wt%, and Fe and inevitable impurities for the rest. It has high CO2 and chlorine ion corrosion resistance at temperature up to 120-150 deg.c, improved impact toughness and relatively low production cost.

Description

110 grade of steel resistant to carbon dioxide, chloride ion corrosion stainless steel steel for oil well pipes

Technical field

The present invention relates to steel for oil well pipes, particularly a kind of high strength, high temperature resistance (120-150 ℃), anti-CO ₂, 110 grade of steel steel for oil well pipes under the chloride ion corrosion condition.

Background technology

API standard L80-13Cr tubing and casing intensity is the 80-95 grade of steel, and the highest service temperature is generally 120 ℃, and corrosion resisting property is less than 0.25mm/y, uses in well depth is no more than 4000 meters oil gas well.Along with the exploitation of oil well and gas well, well depth is also in continuous increase, and well depth surpasses the CO that is rich in of 5000m ₂And the oil gas well that surpasses API standard 13Cr steel pipe service condition constantly increases, is badly in need of anti-higher service temperature (120-150 ℃), corrosion resisting property better, the higher tubing and casing of intensity is as 110 steel grade oil sleeve pipes.For satisfying high intensity and high anti-corrosion requirement, abroad each big steel pipe factory develops 110 nonstandard grade of steel 13Cr stainless steel tubing and casing one after another, and as the KO-HP1-13Cr110 of Kawasaki, the low-carbon (LC) SM13CR110 of Sumitomo etc., its chemical ingredients and performance are as shown in table 1.

Table 1 Kawasaki and Sumitomo 110 steel grade oil sleeve pipe chemical ingredientss

The trade mark	Chemical composition(wt％)
													C		Si	Mn		Cr		Ni	Mo		P	S
	SM13CR	≤ 0.03		≤0.5	≤1.0		11.0-14.0		4.0-6.0	0.2-1.2		≤ 0.020													≤ 0.010
KO-HP1-13Cr													≤ 0.04		≤0.5	≤0.6		12-14		3.5-4.5	0.8-1.5		≤ 0.020	≤ 0.010
	Grade of steel		Yield strength					Rm			Unit elongation (%)
Minimum Kpsi (Mpa)														Maximum Kpsi (Mpa)		Minimum tensile strength Kpsi (Mpa)
			KO-HP1-13Cr110		110(758)			130(896)		120(792～827)									The API standard
SM13CRS110		110(758)											130(896)		115～120(792～827)			The API standard

The existing corrosion-resistant alloy oil annular tube steel of using is referring to table 2, wherein the spy opens flat 11-140594 and does not relate to requirement of strength, a requirement of strength surpasses 110 grade of steel (2003-105441,95～125Kpsi,-40, more than the 30J), but undeclared environment for use, an intensity is 80 grade of steels, and other 4 requirement of strength also all are no more than 110 grade of steels.The nonstandard 13Cr of Kawasaki and Sumitomo company all contains higher nickel and molybdenum and lower carbon, and high Cr alloy partial monopoly of mentioning in the patent such as clear 61-207550, spy open flat 4-224656, spy and open flat 11-140594 etc. and also contain higher nickel and molybdenum.Main by increasing particularly precious metal alloys such as Ni and Mo of alloy content, guarantee high temperature resistant, CO ₂, and micro-H ₂The S corrosive nature.Require high temperature resistant 120-150 ℃, anti-CO for deep-well ₂Corrosion and and do not require H ₂S corrosive environment, tubing and casing cost nickelic, molybdenum alloy is too high.

Table 2

	C	Si	Mn	P	S	Cr	Ni	Mo	Cu	Al	N	B(Ti)	V	Fe
															Clear 61-207550 (100 grade of steel)	0.03 /0.20	≤1.0	≤1.0			12 /14	0.5 /6	0.5 /4.0				≤ 0.006		Balance
Te Kaiping 4-224656 (90-100 grade of steel)	0.02 /0.05	≤0.3	0.3/1.2	≤ 0.025	≤ 0.003	12 /14	3 /5	0.5 /1.5		0.01 /0.05	0.03 /0.08			Balance
															Te Kaiping 8-120415 (80 grade of steel)	0.15 /0.22	≤1.0	0.25 /1.0	≤ 0.020	≤ 0.010	12 /14				≤0.03	0.015 /0.03			Balance
Te Kaiping 11-140594 (nothing)	≤ 0.05	≤0.5	≤1.5	≤0.03	≤ 0.001	10 /14	4 /7	1 /3	1 /2	0.06 /03	≤0.08	0.5S /0.05		Balance
															Flat 4-88152 (≤100 grade of steel)	0.08 /0.25	≤1.0	≤2.0	≤0.04	≤ 0.01	14 /16	0.5 /3.0	0.1 /1.0			0.03 /0.10		0.05 /0.30	Balance
Clear 61-69947 (≤105 grade of steel)	0.1 /0.3	≤1.0	≤2.0			12.5 /13.5					≤0.02	(Ti) a small amount of	On a small quantity	Balance
															The spy opens 2003-105441 (95～125 grade of steel) (40, more than the 30J)	0.15 /0.25	≤1.0	0.1 /1.0	≤0.03	≤ 0.005	11 /14	≤0.5			≤0.1	≤0.07		≤0.15	Balance

Summary of the invention

In view of existing API standard L80-13Cr (0.2C-13Cr) oil well pipe intensity can not satisfy the deep-well requirement, and low-carbon (LC) 13Cr high alloy oil annular tube steel contains precious metal alloys such as higher Ni and Mo, cost is very high, the object of the present invention is to provide a kind of 110 grade of steel resistant to carbon dioxide, chloride ion corrosion stainless steel steel for oil well pipes, replacing present general nickel-molybdenum is low carbon stainless steel, solves deep-well oil-gas field tubing and casing material.

For achieving the above object, technical scheme of the present invention is,

110 grade of steel resistant to carbon dioxide, chloride ion corrosion stainless steel steel for oil well pipes, its composition quality per-cent is:

C：0.05～0.18

Si：0.2～1.00

Mn：0.20～1.00

Cr：10.0～14.0

Ni：0.5～3.0

Cu：0.5～1.5

V：0.03～0.08

All the other are Fe and unavoidable impurities element.

In addition, anti-CO of the present invention ₂, chloride ion corrosion stainless steel steel for oil well pipes also comprises Mo:0.1-0.5, by mass percentage.

By Electric furnace steel making and forging (or rolling) cogging, pipe is behind perforation, hot rolling, thermal treatment, hydraulic test and carry out whole modified thermal treatment and pipe end processing with steel of the present invention, and being up to the standards through body just can be made into qualified tubing and casing product.

C: be the bioelement that guarantees steel strength performance and corrosive nature.For guaranteeing necessary strength, carbon content can not be low excessively, hardening capacity and undercapacity when carbon content is lower than 0.01wt%; Carbon content is higher than 0.2%, causes in the tissue reducing crystal boundary chromium content because of carbon and chromium form carbide, reduces corrosion resistance.Simultaneously, carbon content is too high, the hardness height of material, and toughness degenerates, and solidity to corrosion will be affected the suitable restriction of needs carbon content.

Cr: be the main alloy element that improves solidity to corrosion and intensity.Cr content is less than 10% o'clock, the solidity to corrosion deficiency, and Cr content was greater than 14% o'clock, and the intensity and the hardness of material are too high, cause the toughness of material to descend.The too high plain body of high temperature iron that also easily causes of chromium forms, and reduces hot workability.

Ni: improve corrosive nature and toughness, help high temperature rolling, reduce forming high temperature delta ferrite tendency.Useful to reducing Cold Brittleness Transition Temperature simultaneously.The Ni add-on is low excessively, DeGrain, the too high cost that then increases of add-on.

Cu: at CO ₂Form protective membrane in the medium, improve corrosion resisting property.Less than 0.1%, it is not obvious that the copper amount is crossed low effect, surpasses 2%, is prone to crystal boundary and separates out, and worsens processing characteristics.The copper solid solution is in nickel, generally according to Ni: Cu is 1: 2～3 comparatively reasonable.Copper and nickel are the austenite stable element equally, and is favourable to suppressing the high temperature delta ferrite and improving solidity to corrosion.

Si: add and play deoxidation in the steel and improve corrosion proof effect, be lower than 0.1%, DeGrain, greater than 1%, processing and toughness worsen.

Mn: improve the element of the obdurability of steel, not obvious less than effect in 0.1% o'clock, greater than 2%, will reduce corrosive nature.

V: but vanadium crystal grain thinning, raising hardening capacity added, obviously improve the strength of materials.Less than 0.01%, act on not obviously, greater than 0.10% because the precipitate alligatoring, will cause hardness too high, processing characteristics and toughness will worsen.

Mo: improve corrosion-resistant particularly anti-local corrosion performance.Molybdenum also helps intensity and the hardening capacity that improves material.Add-on is lower than 0.01%, and DeGrain surpasses 0.5%, increases product cost.

Compared with prior art, the requirement of strength of existing alloy all is no more than 110 grade of steels.The nonstandard 13Cr of above-mentioned Kawasaki and Sumitomo company all contains higher nickel and molybdenum and lower carbon, and high Cr alloy partial monopoly of mentioning in the patent such as clear 61-207550, spy open flat 4-224656, spy and open flat 11-140594 etc. and also contain higher nickel and molybdenum.It mainly by increasing particularly precious metal alloys such as Ni and Mo of alloy content, guarantees high temperature resistant, CO ₂, and micro-H ₂The S corrosive nature.Require high temperature resistant 120-150 ℃, anti-CO for deep-well ₂Corrosion and and do not require H ₂S corrosive environment, tubing and casing cost nickelic, molybdenum alloy is too high.The present invention only adds a certain amount of nickel (adding the 0.1-0.5%Mo effect simultaneously more), copper and trace vanadium and reaches 110 grade of steel intensity by on API standard L80-13Cr tubing and casing composition basis, satisfies anti-120-150 ℃ simultaneously, CO ₂And chloride ion corrosion requirement.

A, open flat 4-224656 patent with clear 61-207550 patent, spy and compare, the present invention is by adding the molybdenum (0.5-4%) that lower-cost copper, vanadium and a small amount of molybdenum (being not more than 0.5%) replace high level in the contrast patent, not only can guarantee corrosive nature (chloride ion corrosion), improve mechanical property, can also reduce production costs simultaneously.

B, open flat 8-120415 patent with the spy and compare, the present invention contains a spot of molybdenum and helps improving the anti-chlorine ion corrosion performance, improve mechanical property by adding vanadium,, overcome the deficiency of contrast patented product machinery and corrosive nature by adding nickel, copper raising corrosion resistance nature.

C, open flat 11-140594 patent with the spy and compare, the present invention has replaced higher nickel (4-7%) and molybdenum raising mechanical property in the contrast patent alloy designs by carrying high-carbon quantity and adding vanadium.Simultaneously,, further improve pitting resistance, by the cost of compound adding alloy reduction product by adding a small amount of molybdenum because this steel for oil well pipes is only required intensity and resistant to carbon dioxide, chloride ion corrosion requirement.

D, compare with flat 4-88152 patent, the present invention contrasts patent and has reduced chromium content, adds copper and guarantees corrosive nature and improve mechanical property, can also reduce production costs simultaneously.

E, compare with clear 61-69947 patent, patent of the present invention improves mechanical property by adding vanadium, improve corrosion resistance nature by adding copper, nickel, molybdenum, has overcome the deficiency of the corrosion-resistant and mechanical property of contrast patented product.

F, open the 2003-105441 patent with the spy and compare, the contrast patent only contains a certain amount of chromium and a spot of nickel, can not satisfy the anti-CO under 120-150 ℃ ₂And chloride ion corrosion performance requriements.The present invention by add lower-cost copper, a spot of molybdenum is guaranteed anti-CO ₂And the chloride ion corrosion performance, copper also helps improving mechanical property and reducing production costs.

Beneficial effect of the present invention

External high strength anti carbonic acid gas, the main alloy designs of chloride ion corrosion oil annular pipe are by changing the carbon dioxide corrosion resistant tubing and casing that methods such as some alloy composition such as low-carbon (LC), nickel, the compound interpolation of molybdenum obtain 110 grade of steels on the APIL80-13Cr basis.

The present invention not only can obtain the oil well pipe that strength grade reaches 110 grade of steels by alloying elements such as nickel, copper and a small amount of molybdenum, vanadium, and, owing to nickel, copper compound action, improved the high temperature resistant carbon dioxide corrosion ability of tubing and casing.The compound interpolation nickel of this alloy, copper also have effect to the impelling strength of improving material.In the alloy designs by controlling certain carbon content, add chromium, nickel, copper, vanadium and add element such as a small amount of molybdenum and, obtaining anti-CO under 120-150 ℃ of condition of temperature through after the suitable thermal treatment ₂Reach the tubing and casing of 110 grade of steels with the intensity of chloride ion corrosion, nickelic, the serial 110 steel grade oil shell materials of molybdenum of the low-carbon (LC) that uses can be saved the nickel of 1-2% and the molybdenum of 1-2% at present, reduce cost greatly.

Embodiment

Table 3 is depicted as the chemical ingredients of the embodiment of the invention, reaches the tubing and casing alloy that generally use in present oil field as a comparison case.

Table 3

	Chemical ingredients (wt%)
											C	Si	Mn	P	S	Cr	Mo	Ni	Cu	V
	Embodiment 1	0.084	0.49	0.45	0.018	0.005	12.3		2.74	1.42											0.04
Embodiment 2											0.11	0.59	0.58	0.018	0.004	12.7		1.97	1.13	0.06
	Embodiment 3	0.18	0.55	0.48	0.011	0.0009	12.6		1.50	1.45											0.05

Embodiment 4	0.16	0.52	0.83	0.011	0.0007	13.2		2.92	1.50	0.08
											Embodiment 5	0.12	0.79	0.64	0.015	0.003	11.7		2.53	0.98	0.06
Embodiment 6	0.14	0.40	0.70	0.020	0.003	12.5	0.1	2.00	0.70	0.05
											Embodiment 7	0.058	0.20	1.00	0.011	0.0007	10.0	0.2	1.01	0.50	0.03
Embodiment 8	0.10	1.00	0.20	0.015	0.003	14.0	0.5	3.00	0.60	0.07
											Comparative example 1	0.02	0.46	0.35	0.010	0.0033	13.6	1.1	4.61
Comparative example 2	0.02	0.42	0.38	0.011	0.0036	12.3	2.03	5.8	1.48
											Comparative example 3	0.03	0.21	0.36	0.018	0.002	12.8	1.07	4.22

Table 4 is the mechanical property of steel of the present invention and Comparative Examples steel and resistant to carbon dioxide, chloride ion corrosion performance.Corrosion experiment adopts autoclave, and under 120 ℃ and 150 ℃ of temperature, partial pressure of carbon dioxide 2.5MPa also adds 3.5%NaCl to corrosion experiment respectively, velocity of medium is set at 2m/S, experimental period is 168 hours, measures corrosion weight loss and converts erosion rate to, the mm/a of unit.

Table 4

	Rt0.6(MPa)	Rm(MPa)	A50.8(％)	Erosion rate mm/a (120 and 150 ℃, 2.5Mpa CO 2+ 3.5%NaCl, speed 2m/S)
						Embodiment 1	772	895	21.0	0.039	0.002
Embodiment 2	779	1044	17.0	0.045	0.002
						Embodiment 3	781	1040	17.0	0.038	0.003
Embodiment 4	853	1085	19	0.042	0.002
						Embodiment 5	797	956	19.5	0.047	0.002
Embodiment 6	820	960	19.0	0.040	0.002

Comparative example 1	815	868	20.5	0.036	0.002
						Comparative example 2	821	920	20.5	0.025	0.001
Comparative example 3	835	941	17.0	0.032	0.002

From the result of table 4 as can be seen, the intensity and the corrosion resistance nature of high-alloy stainless steel oil annular tube steel high temperature resistant of the present invention, carbonic acid gas and chloride ion corrosion performance and ultralow-carbon chromium, molybdenum high-alloy stainless steel oil annular tube steel are suitable.The present invention through after Electric furnace steel making, die casting (or continuous casting), forging (or rolling) cogging, rolling tubulation and the rational heat treatment technology, can obtain the anti-corrosion tubing and casing of non-API that mechanical property satisfies 110 grade of steels with steel.By reducing nickel content and suitably adding a small amount of molybdenum alloy element and can improve corrosive nature and reduce material cost.

Claims (2)

1.110 grade of steel resistant to carbon dioxide, chloride ion corrosion stainless steel steel for oil well pipes, its composition quality per-cent is:

C： 0.05～0.18

Si：0.2～1.00

Mn：0.20～1.00

Cr：10.0～14.0

Ni：0.5～3.0

Cu：0.5～1.5

V： 0.03～0.08

All the other are Fe and unavoidable impurities element.

2. 110 grade of steel resistant to carbon dioxide as claimed in claim 1, chloride ion corrosion stainless steel steel for oil well pipes is characterized in that, also comprise Mo:0.1～0.5, by mass percentage.