EP0615551A1

EP0615551A1 - Weldable high-strength structural steel with 13 % chromium.

Info

Publication number: EP0615551A1
Application number: EP92923679A
Authority: EP
Inventors: Hagen Ingo Von; Rolf Poepperling; Hubertus Schlerkmann; Ulrike Zeislmair
Original assignee: Mannesmann AG
Current assignee: Vodafone GmbH
Priority date: 1991-12-05
Filing date: 1992-11-23
Publication date: 1994-09-21
Anticipated expiration: 2012-11-23
Also published as: CN1077230A; NO302302B1; BR9206853A; CA2125178A1; RU94030489A; ES2098556T3; WO1993011270A1; US5462615A; DE59208076D1; NO941164D0; NO941164L; ATE149211T1; JPH07501581A; EP0615551B1; RU2102521C1

Abstract

PCT No. PCT/DE92/00987 Sec. 371 Date Jul. 25, 1994 Sec. 102(e) Date Jul. 25, 1994 PCT Filed Nov. 23, 1992 PCT Pub. No. WO93/11270 PCT Pub. Date Jun. 10, 1993.Disclosed is a process for producing seamless steel pipes or flat products (strip or sheet) for pipes or vessels which are intended for the conveyance, transport or processing of gaseous or liquid hydrocarbons containing CO2 and water and possibly small proportions of H2S and are resistant to stress crack corrosion and have good welding properties at the same time and a 0.2-percent elongation limit of at least 450 N/mm2. The process uses a nickel-containing steel of the following composition (percent by weight): min. 0.015% C, 0.15-0.50% Si, max. 2.00% Mn, max. 0.020% P, max. 0.003% S, 12.0-13.8% Cr, 0.002-0.02% N, 0.01-0.05% Nb, remainder iron and usual impurities. It is presently suggested that the nickel content is limited to a maximum of 0.25%, the manganese content amounts to at least 1.0%, the carbon content is limited to 0.035%, and 0.01 to 1.2% molybdenum is contained as additional alloying component.

Description

Weldable high-strength structural steel with 13% chrome

The invention relates to a method for producing seamless steel tubes or flat products (strip and sheet) for tubes or

Containers that are intended for the conveyance, transport or processing of hydrocarbons. In the presence of CO ₂ and water and possibly small amounts of H ₂ S, there are corrosive conditions in the media to be transported or processed.

For the production of hydrocarbons under corrosive conditions, pipes made from low-alloy steels with passive corrosion protection (inhibition) are usually made from high-alloy

Corrosion-resistant steels are used to meet the high requirements with regard to corrosion resistance, especially the

Resistance to stress corrosion cracking. A suitable steel can be found, for example, in DE 26 15 599 C2. Because of the high proportions of expensive alloying elements (for example 22% Cr, 5% Ni, 3% Mo), pipes and containers made from such steels are extremely cost-intensive for the above-mentioned applications. These relatively high-strength duplex steels usually have low C contents and are therefore easy to weld. Steels containing 0.18 - 0.22% C and 12.5 - 1.% Cr are also known for use in oil fields (material RISI 420). This material has very good corrosion resistance in a humid CO ₂ environment. Since pipes made of this material are practically not weldable under construction site conditions, only the pipes are connected

Screw connections to use. Pipes made of this steel are therefore only used as delivery pipes, but not as line pipes. If traces of H ₂ S are also contained in the hydrocarbons to be conveyed through the pipes, stress corrosion cracking can result, since this material is only comparatively minor

Resistant to this type of corrosion.

Furthermore, 13% chromium steels are known for the production of steel pipes, which are weldable. An example of this is the material RISI 410 (material no. 1.4006), which 0.06 - 0.12% C, max. Contains 1.0% Mn and 12.0 - 14.0% Cr. The weldability of this steel is

guaranteed because of the lower carbon content. However, the heat treatment of the products produced from them is often problematic

Rolled products, as this often leads to an inhomogeneous structure, which is responsible for the very poor resistance of these steels to stress corrosion cracking in the presence of H ₂ S. For this reason, this material, which is to be regarded as rust and acid resistant, is used for pump pipes, heat exchangers and the like, but is not used for the production of hydrocarbons; it is only used as a cast or forged product for fittings in the area of

Wellhead used. Its low corrosion resistance is sufficient through reports of damage cases in the literature

documented. Finally, a steel for the production of seamless steel tubes with the following composition is known from JP 57-58.9: max. 0.015% C

0.10-0.80% Si

0.10 - 2.00% Mn

Max. 0.025% P

Max. 0.010% S

11.0 - 17.0% Cr

0.10-3.00% Ni

Max. 0.015% N

0.01-0.05% Nb

0.01-0.10% Al

Balance iron and usual impurities.

This steel is described as weldable, tensile, tough and corrosion-resistant. The seamless steel tubes made from it showed a yield point in the area after heat treatment

428 - 502 N / mm ² . Adherence to the set is crucial for ensuring the corrosion resistance

Upper limits for C with max. 0.015% and N with max. 0.015% viewed. Mo is not provided for in this steel.

In contrast, it was found in the context of the present invention that a steel with the composition specified in claim 1 not only also has excellent properties in terms of

Has corrosion resistance and is well weldable and very tough, but also allows a 0.2% proof stress, which significantly exceeds the values known from JP 57-5849. This is due in particular to the surprising finding that a limitation of the Ni content, which is up to 3.0% in the known steel must be at a maximum value of 0.25%. Under this condition, within the framework of the values mentioned in patent claim 1, contents of C in the range from 0.015% to 0.035% and of N in the range from 0.002 to 0.02% can be permitted for the other alloy elements; This opens up new possibilities with regard to the mechanical properties. In contrast to the known steel, the steel used according to the invention also contains Mo, in the range from 0.01% to 1.2%; this content is advantageously limited to values of at most 0.2 to 0.3%. The minimum content of Mn is 1.0%, while in the known steel, much lower contents of up to 0.1% are permitted for Mn; there is a limit of 2.0%. The Cr solL content is in the range from 12.0 to 13.8%. Values in the range 0.02-0.04% have proven to be particularly favorable for the addition of Nb; however, a range of 0.01-0.05% is permissible. Since the C content is 0.015 - 0.035%

is limited, these steels have good welding properties. For Si a content of 0.15 - 0.50% and for Mn a content of

1.0 - 2.0% prescribed. The impurities on P and S must be max. 0.020% and 0.003% respectively.

The extent to which the content limits of the individual alloy elements specified according to the invention are adhered to is shown, for example, in JP 57-5849 as a comparative example of the invention there

Steel used with the following composition:

0.020% C

0.30% Si

0.52% Mn

0.009% P

0.004% S

0.73% Ni 13.1% Cr

0.026% Nb

0.025% AI

0.011% N

Balance iron and usual impurities.

This 5 steel, which differs from the 5 steel of the present invention in the contents of Mn, Mo and Ni by a maximum of about half each

Percentage point differed, did not prove there

corrosion-resistant.

With regard to the rolling processing of the steel to be used according to the invention, there are several possibilities. In the

Manufacture e.g. of sheets for containers or welded pipes, the primary material should be heated to 1100 - 1250 ° C, then in a first

Pre-rolled in the rolling phase at temperatures above 1000 ° C and then finally rolled in a second rolling phase at temperatures in the range of 850 - 750 ° C with a minimum deformation of 30%.

The second rolling phase is preferably carried out in such a way that, when accelerated from a final rolling temperature of greater than or equal to 850 ° C., the cooling rate is at least 5 K / s to below 200 ° C. Further cooling can take place in air. Subsequent starting is recommended, but is not absolutely necessary.

In another advantageous process variant of the invention, the cooling is carried out from a final rolling temperature greater than or equal to 650 ° C. with a cooling rate from 0.5 to 2 K / s to ambient temperature.

In order to selectively set narrow ranges in the strength values or products (e.g. 15 ksi), these can be heat-treated in a separate process step in a manner known per se.

The invention is explained in more detail below with reference examples and test results. Figures 1 and 2 show measurement results with regard to the erosive corrosion for different steels under different conditions.

Table 1 shows the chemical compositions of three different 13% chromium steels with the designations 410, 411 and 413. Steel 410 corresponds to the present invention, while the other steels are to be regarded as comparative examples. Steel 411 differs from the invention in that the Ni content is 2.03%, and that in 5steel 413 is 0.57% Mn content and Ni content 4.19%. Table 2 shows the mechanical and technological properties for under

reproduced flat products and pipes manufactured under different rolling and heat treatment conditions. A TM-rolled sheet, which was used at 1140 ° C and finally rolled at 800 ° C, achieved the excellent mechanical properties shown in the first line under work number 410A without any tempering treatment. By lowering the final rolling temperature to 750 ° C (work number 410B), the strength values could be increased even further, although the toughness properties deteriorated slightly. From the in the lower part of table 2 (work numbers 410.1 to 410.5)

The test results shown show the influence of heat treatment by hardening and tempering under different conditions under the same rolling conditions. You can clearly see that

considerable increases in the values achieved with regard to the strength and toughness properties.

Table 3 shows that the steel 410 according to the invention with respect to its

Resistance to stress corrosion cracking of the well known steels 411 and

413 is clearly superior.

Only under very extreme test conditions (0.01 bar H ₂ S and 5%

NaCl), the round tensile test failed in steel 410

1000 hours with a load of 90% R _{p 0.2} . The comparison steels showed sample failures even under much milder test conditions.

FIGS. 1 and 2 show the resistance of the steel according to the invention to abrasive corrosion under different conditions in comparison to the steels 411 and 413 and a steel X20Cr 13. Taking into account the analysis values from Table 1, it can be seen that the increased content of Ni and in particular Mo the

Reduce the rate of corrosion in the event of abrasive corrosion. However, the resistance of the steel 410 according to the invention is, in particular, that of

Comparison with the steel X20Cr 13 shows, still quite good. Despite their better resistance to abrasive corrosion, they are

Comparative steels 411 and 413, as can be seen from Table 3, with their increased Ni and Mo contents are significantly inferior to the steel according to the invention in terms of resistance to stress corrosion cracking,

Surprisingly, the reason for the success according to the invention is the drastic limitation of the Ni and Mo contents. In the event that the stress corrosion cracking resistance to the

Resistance to abrasive corrosion a much greater

The Mo content should even be limited to values below 0.2%.

Table 3: Results of stress corrosion cracking tests

Round tensile tests under constant load

Load: 90% Rpo. 2

Test duration: 1000 h

Carrier gas: CO ₂ under normal pressure

Symbols: O: no findings: X: sample failure

n.g .: not checked

Claims

1. Process for the production of seamless steel pipes or

Flat products CBand or sheet metal) for pipes or containers used for the conveyance, transport or processing of gaseous or liquid hydrocarbons, the CO ₂ and water as well

optionally contain small amounts of H ₂ S, are determined and are resistant to stress corrosion cracking and at the same time are easy to weld and have a 0.2% proof stress of at least 450 N / mm, using a Ni-containing steel, the following Composition (% by weight): min. 0.015% C

0.15 0.50% Si

Max. 2.00% Mn

Max. 0.020% P

Max. 0.003% 5

12.0 - 13.8% Cr

0.002 - 0.02% N

0.01-0.05% Nb

Remainder iron and usual impurities, characterized in that the Ni content to max. 0.25% is limited that the Mn content is at least 1.0%, the C content to 0.035. is limited and that as an additional alloy component 0.01 - 1.2% Mo

is included.

2. The method according to claim 1,

characterized,

that the Mo content is limited to a maximum of 0.20%.

3. The method according to any one of claims 1 to 2,

characterized,

that the Nb content is adjusted to a value between 0.02% and 0.04%.

4. Process for the production of flat products according to one of the

Claims 1 to 3,

characterized,

that the primary material is heated to 1100 to 1250 ° C, then pre-rolled in a first rolling phase at temperatures down to a maximum of 1000 ° C and then in a second rolling phase

Temperatures in the range of 650 - 700 ° C with a minimum deformation of 30%.

Method according to one of claims 1 to 3,

characterized,

that from a final rolling temperature of at least 650 ° C

accelerates with a cooling rate of at least 5 K / s to below

200 ° C is cooled.

6. The method according to claim 5,

characterized,

that is started separately after the accelerated cooling.

7. The method according to any one of claims 1 to 3,

characterized,

that from a final rolling temperature of at least 850 ° C with a cooling rate of 0,

5 to 2 K / s until it is cooled to ambient temperature.

6. The method according to any one of claims 1 to 4 or 7,

characterized,

that the rolled products to set the desired

Strength level to be subjected to a separate heat treatment.