WO2010043375A1 - Nickel-chrom-legierung - Google Patents
Nickel-chrom-legierung Download PDFInfo
- Publication number
- WO2010043375A1 WO2010043375A1 PCT/EP2009/007345 EP2009007345W WO2010043375A1 WO 2010043375 A1 WO2010043375 A1 WO 2010043375A1 EP 2009007345 W EP2009007345 W EP 2009007345W WO 2010043375 A1 WO2010043375 A1 WO 2010043375A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alloy
- nickel
- chromium
- aluminum
- iron
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
Definitions
- petrochemicals require materials that are both temperature- and corrosion-resistant and, in particular, are able to cope with the hot product and also the hot combustion gases, for example from steam crackers.
- Their coils are subject to external oxidizing aufstickenden combustion gases with temperatures up to 1100 C C and more and in the interior at temperatures up to about 900 ° C and optionally also high pressure of a carburizing and oxidizing atmosphere.
- the carburizing hydrocarbon atmosphere inside the pipes is associated with the danger that diffuses from there the carbon in the pipe material, the carbides in the material and increase from the existing carbide M 23 C 9 with increasing carburizing the carbon-rich carbide M 7 C 6 forms.
- the consequence of this is internal stresses due to the increase in carbide volume associated with carbide formation or conversion and a reduction in the strength and toughness of the pipe material.
- US Pat. No. 5,306,358 discloses a WG-weldable nickel-chromium-iron alloy containing up to 0.5% carbon, 8 to 22% chromium, up to 36% iron, up to 8% manganese, silicon and niobium , up to 6% aluminum, up to 1% titanium, up to 0.3% zirconium, up to 40% cobalt, up to 20% molybdenum and tungsten and up to 0.1% yttrium, balance
- German patent specification 103 02 989 describes a nickel-chromium casting alloy which is also suitable as a material for coils of cracking and reforming furnaces with up to 0.8% carbon, 15 to 40% chromium, 0.5 to 13% iron, 1, 5 to 7% aluminum, to 0.2% silicon, to 0.2% manganese, 0.1 to 2.5% niobium, to 11% tungsten and molybdenum, to 1, 5% titanium, 0.1 to 0.4% zirconium and 0.01 to 0.1% yttrium, balance nickel.
- This alloy has proved to be quite useful especially when used as a pipe material, although the practice continues to call for pipe materials with a longer service life.
- the invention is therefore directed to a nickel-chromium alloy having improved durability under conditions such as cracking and reforming of hydrocarbons.
- the solution to this problem consists in a nickel-chromium alloy with 0.4 to 0.6% carbon, 28 to 33% chromium, 15 to 25% iron, 2 to 6% aluminum, each up to 2% silicon and manganese, respectively to 1, 5% niobium and tantalum, each to 1, 0% tungsten, titanium and zirconium, in each case to 0.5% yttrium and cerium, to 0.5% molybdenum and to 0.1% nitrogen remainder including smelting-related impurities nickel.
- this alloy contains, individually or side by side, 17 to 22% iron, 3 to 4.5% aluminum, in each case 0.01 to 1% silicon, to 0.5% manganese, 0.5 to 1, 0% niobium, bis 0.5 tantalum, to 0.6% tungsten, 0.001 to 0.5% titanium each, to 0.3% zirconium, to 0.3% yttrium, to 0.3% cerium, 0.01 to 0.5% Molybdenum and 0.001 to 0.1%
- the alloy according to the invention is characterized in particular by its comparatively high contents of chromium and nickel as well as a mandatory carbon content within a comparatively narrow range.
- the silicon improves the oxidation and carburization resistance.
- the manganese also has a positive effect on the oxidation resistance and, in addition, has a favorable effect on the weldability, the melt deoxidizes and stably binds the sulfur.
- Niobium improves creep strength, forms stable carbides and carbonitrides; It also serves as a mixed crystal hardener. Titanium and Tantalum improve creep strength. Even at very low levels, very finely divided carbides and carbonitrides form. At higher levels, titanium and tantalum act as mixed crystal hardeners.
- Tungsten improves the creep rupture strength. Particularly at high temperatures, tungsten improves the strength by means of solid solution hardening, since the carbides partly dissolve at higher temperatures.
- Cobalt also improves the creep rupture strength by means of solid solution hardening
- Yttrium and cerium obviously not only improve the oxidation resistance and especially the adhesion and growth of the Al 2 O 3 cover layer.
- yttrium and cerium improve the creep resistance even at very low levels, since they stably bind the remaining free sulfur.
- Low levels of boron also improve creep strength, prevent sulfur segregation, and retard aging by coarsening the M 23 C 6 carbides.
- Molybdenum also improves the creep rupture strength, especially at high temperatures, by means of solid solution hardening. Especially because at high temperatures, the carbides partially go into solution.
- the nitrogen improves the creep rupture strength by means of carbonitride formation, while hafnium, even at low levels, improves the oxidation resistance by means of better adhesion of the cover layer and has a positive effect on the creep rupture strength.
- Phosphorous, sulfur, zinc, lead, arsenic, bismuth, tin and tellurium are among the impurities, their contents should therefore be as low as possible.
- the alloy is particularly suitable as a casting material for components of petrochemical plants, for example for the production of coils for cracking and reforming furnaces, reformer tubes, but also as a material for iron ore direct reduction plants and similarly loaded components.
- these include furnace parts, radiant tubes for heating ovens, rolls for annealing furnaces, parts of - A -
- the alloy is characterized by high resistance to oxidation and carburization as well as good creep strength and creep resistance.
- the inner surface of cracking or reformer tubes is also characterized by a catalytically inert, aluminum-containing oxide layer, thus preventing the formation of catalytic coke strands, known as carbon nanotubes.
- the properties that characterize the material also remain with multiple burn-out of the coke which inevitably deposits on the inner wall of the pipes during cracking.
- the alloy for producing centrifugally cast tubes if they are drilled with a contact pressure of 10 to 40 MPa, for example 10 to 25 MPa.
- a contact pressure 10 to 40 MPa, for example 10 to 25 MPa.
- a cold deformation or strain hardening of the pipe material takes place in a near-surface zone with depths of, for example, 0.1 to 0.5 mm.
- the cold-worked zone recrystallizes, resulting in a very fine-grained microstructure.
- the recrystallization structure enhances the diffusion of the oxide-forming elements aluminum and chromium, which promotes the formation of a closed layer of high density and stability consisting primarily of alumina.
- the resulting firmly adhering aluminum-containing oxide forms a closed protective layer of the inner wall of the pipe, which is largely free of catalytically active centers, for example of nickel or iron, and even after a prolonged cyclic
- the top layer consists primarily of Al 2 O 3 and the mixed oxide (Al, Cr) 2 O 3 and is largely inert to a catalytic coke formation. It is poor in elements that catalyze coke formation, such as iron and nickel.
- a durable oxide protective layer serves to condition, for example, the inner surface of steam cracker tubes after their installation when the relevant furnace is heated to its operating temperature.
- This conditioning can be carried out as heating with interposed isothermal heat treatments in a furnace atmosphere, which is set during the heating according to the invention, for example in a very weakly oxidizing water vapor-containing atmosphere having an oxygen partial pressure of at most 10 20 , preferably at most 10 30 bar.
- Particularly suitable is a protective gas atmosphere of 0.1 to 10 mol% of water vapor, 7 to 99.9 mol% of hydrogen and hydrocarbon individually or side by side and 0 to 88 mol% noble gases.
- the atmosphere in the conditioning is preferably made of an extremely weak oxidizing mixture of steam, hydrogen, hydrocarbons and inert gases in a quantity ratio such that the oxygen partial pressure of the overall premixture at a temperature of 600 0 C is less than 10 '20 bar, preferably less than 10 30 bar is.
- the initial heating of the tube interior after a previous mechanical removal of a surface layer, ie the separate heating of the resulting cold-formed surface zone is preferably carried out under very low oxidizing inert gas in several phases each at a rate of 10 to 100 ° C / h initially to 400 bis 750 0 C, preferably about 550 0 C at the the inner surface of the tube.
- This heating phase is followed by a one to fifty-hour hold within the temperature range mentioned.
- the heating takes place in the presence of a water vapor atmosphere as soon as the temperature has reached a value which precludes the formation of condensed water. Following this holding, the tube is then brought to the operating temperature, for example to 800 to 900 0 C and is ready for use.
- the tube temperature gradually increases in the cracking operation as a result of the deposition of pyrolytic coke and finally reaches on the inner surface about 1000 0 C or even 1050 0 C.
- This temperature which essentially converts Al 2 O 3 and to a small extent from (Al, Cr ⁇ O ß existing inner layer of a transition oxide such as Y, ⁇ - or ⁇ - Al 2 O 3 in stable ⁇ -alumina to.
- the tube has reached its operating state with its mechanically removed inner layer in a multi-stage, but preferably eintoxicityen method.
- the process does not necessarily have to run in one stage, but can also start with a separate preliminary stage.
- This precursor involves initial heating after ablation of the inner surface to hold at 400 to 750 ° C.
- the pipe pretreated in this way can then be further treated in situ in another factory, for example, starting from its cold state in the manner described above, ie brought to the operating temperature in the installed state.
- the mentioned separate pre-treatment is not limited to tubes, but is also suitable for a partial or complete conditioning of surface zones of other workpieces, which are then treated according to their nature and use as in the invention or by other methods, but with a defined initial state.
- alloy 9 is also characterized by a high carburization resistance; because, according to the diagram of FIG. 2, it has the lowest weight gain after all three carburizing treatments, compared with the conventional alloys 12 and 13, due to the low weight gain.
- FIGS. 3a and 3b show that the creep rupture strength of the nickel alloy 11 according to the invention is even better in a substantial range than in the two comparative alloys 12 and 13.
- An exception here is the alloy 15, which is not covered by the invention because of its low iron content with, however, much lower oxidation, carburization and coking resistance.
- the creep strength of the alloy 11 is far better than that of the comparative alloy 12. Furthermore, in the simulation series of a cracking operation several pipe sections of a nickel alloy according to the invention were used in a laboratory plant to carry out heating experiments with different gas atmospheres and heating conditions, which followed a thirty minute cracking at a temperature of 900 0 C, the initial phase of the catalytic coke formation , and to investigate and assess the tendency for catalytic coke formation.
- Figures 5 and 6 Examples of the surface finish of the tube interior of furnace tubes with the composition of the invention falling alloy 8 are shown in Figures 5 and 6.
- Figure 6 (Experiment 7 to Table II) shows the superiority of a surface after a conditioning according to the invention in comparison to Figure 5, which relates to a not according to the invention conditioned surface (Table II, Experiment 2).
- the micrograph of the image 7 in the form of the dark areas shows the large-area and thus large-volume result of internal oxidation on the inside of a tube in a conventional nickel-chromium casting alloy compared to the micrograph of the image 8 of the alloy 9 according to the invention, which is practical was not subject to internal oxidation, although both samples were similarly subjected to multiple cyclic treatment from cracking on the one hand and removal of the carbon deposits on the other.
- FIG. 11 relates to an SEM top view of the conventional sample shown in Figure 7 in section; Due to the missing cover layer, it shows a catastrophic oxidation and a corresponding catastrophic formation of catalytic coke in the form of carbon nanotubes.
- the stability of the oxide layer on an alloy according to the invention is particularly clear from the course of the aluminum concentration over the depth of the edge zone after ten cracking phases with respective removal of the
- the stability of the aluminum-containing oxide layer was also investigated by long-term tests in a laboratory plant under process-related conditions.
- the samples of alloys 9 and 11 according to the invention were heated to 950 ° C. under steam and then subjected to cracking at this temperature three times in each case for 72 hours; they were then each subjected to burnout at 900 0 C for four hours.
- the picture 12 shows the closed aluminum-containing
- the nickel-chromium-iron alloy according to the invention is characterized, for example, as a pipe material after removal of the inner surface under mechanical pressure and subsequent multi-stage in situ heat treatment for conditioning the inner surface by a high oxidation, corrosion and in particular by a high creep rupture strength and creep resistance.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims
Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/124,016 US9249482B2 (en) | 2008-10-13 | 2009-10-13 | Nickel-chromium-alloy |
KR1020117008378A KR101738390B1 (ko) | 2008-10-13 | 2009-10-13 | 니켈 크롬 합금 |
JP2011531390A JP2012505314A (ja) | 2008-10-13 | 2009-10-13 | ニッケル−クロム−合金 |
CA2740160A CA2740160C (en) | 2008-10-13 | 2009-10-13 | Nickel chromium alloy |
EP19172613.2A EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
PL17207317T PL3330390T3 (pl) | 2008-10-13 | 2009-10-13 | Stop niklowo-chromowy |
BR122016030244A BR122016030244A2 (pt) | 2008-10-13 | 2009-10-13 | Ligas de niquel-cromo |
ES09744619.9T ES2661333T3 (es) | 2008-10-13 | 2009-10-13 | Aleación de níquel-cromo |
KR1020177013029A KR102029019B1 (ko) | 2008-10-13 | 2009-10-13 | 니켈 크롬 합금 |
EA201170560A EA020052B1 (ru) | 2008-10-13 | 2009-10-13 | Хромоникелевый сплав |
EP09744619.9A EP2350329B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
UAA201106001A UA109631C2 (xx) | 2008-10-13 | 2009-10-13 | Нікель-хромовий сплав |
KR1020197035927A KR102080674B1 (ko) | 2008-10-13 | 2009-10-13 | 니켈 크롬 합금 |
MX2011003923A MX2011003923A (es) | 2008-10-13 | 2009-10-13 | Aleacion de niquel-cromo. |
BRPI0920279-0A BRPI0920279B1 (pt) | 2008-10-13 | 2009-10-13 | Liga de níquel-cromo com alta resistência à oxidação e carburação, resistência à ruptura a longo prazo e resistência à fluência, método para pelo menos parcialmente condicionar objetos feitos da referida liga de níquel-cromo e uso da referida liga de níquel-cromo |
EP17207317.3A EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
KR1020197028227A KR102064375B1 (ko) | 2008-10-13 | 2009-10-13 | 니켈 크롬 합금 |
CN2009801407879A CN102187003B (zh) | 2008-10-13 | 2009-10-13 | 镍铬合金 |
PL09744619T PL2350329T3 (pl) | 2008-10-13 | 2009-10-13 | Stop niklowo-chromowy |
ZA2011/02259A ZA201102259B (en) | 2008-10-13 | 2011-03-25 | Nickel-chromium alloy |
IL212098A IL212098A (en) | 2008-10-13 | 2011-04-03 | Nickel-chrome alloy |
US14/976,389 US10053756B2 (en) | 2008-10-13 | 2015-12-21 | Nickel chromium alloy |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008051014A DE102008051014A1 (de) | 2008-10-13 | 2008-10-13 | Nickel-Chrom-Legierung |
DE102008051014.9 | 2008-10-13 |
Related Child Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17207317.3A Previously-Filed-Application EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
US13/124,016 A-371-Of-International US9249482B2 (en) | 2008-10-13 | 2009-10-13 | Nickel-chromium-alloy |
US14/976,389 Continuation US10053756B2 (en) | 2008-10-13 | 2015-12-21 | Nickel chromium alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010043375A1 true WO2010043375A1 (de) | 2010-04-22 |
Family
ID=41491665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/007345 WO2010043375A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Country Status (20)
Country | Link |
---|---|
US (2) | US9249482B2 (de) |
EP (3) | EP2350329B1 (de) |
JP (4) | JP2012505314A (de) |
KR (4) | KR102080674B1 (de) |
CN (1) | CN102187003B (de) |
BR (2) | BR122016030244A2 (de) |
CA (1) | CA2740160C (de) |
DE (1) | DE102008051014A1 (de) |
EA (1) | EA020052B1 (de) |
ES (2) | ES2661333T3 (de) |
HU (2) | HUE046718T2 (de) |
IL (1) | IL212098A (de) |
MX (1) | MX2011003923A (de) |
MY (1) | MY160131A (de) |
PL (2) | PL2350329T3 (de) |
PT (2) | PT2350329T (de) |
TR (1) | TR201802979T4 (de) |
UA (1) | UA109631C2 (de) |
WO (1) | WO2010043375A1 (de) |
ZA (1) | ZA201102259B (de) |
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DE102008051014A1 (de) * | 2008-10-13 | 2010-04-22 | Schmidt + Clemens Gmbh + Co. Kg | Nickel-Chrom-Legierung |
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- 2009-10-13 EP EP17207317.3A patent/EP3330390B1/de active Active
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US11674212B2 (en) | 2014-03-28 | 2023-06-13 | Kubota Corporation | Cast product having alumina barrier layer |
EP3124645B1 (de) | 2014-03-28 | 2019-10-23 | Kubota Corporation | Giessprodukt mit aluminiumoxidsperrschicht |
WO2018036797A1 (de) * | 2016-08-22 | 2018-03-01 | Siemens Aktiengesellschaft | Sx-nickel-legierung mit verbesserten tmf-eigenschaften, rohmaterial und bauteil |
EP3287535A1 (de) * | 2016-08-22 | 2018-02-28 | Siemens Aktiengesellschaft | Sx-nickel-legierung mit verbesserten tmf-eigenschaften, rohmaterial und bauteil |
US11440106B2 (en) | 2016-10-26 | 2022-09-13 | Schmidt + Clemens Gmbh + Co. Kg | Deep hole drilling method as well as tool for a deep hole drilling machine and deep hole drilling machine |
DE102016012907A1 (de) | 2016-10-26 | 2018-04-26 | Schmidt + Clemens Gmbh + Co. Kg | Tieflochbohrverfahren sowie Werkzeug für eine Tieflochbohrmaschine und Tieflochbohrmaschine |
WO2018078030A1 (de) | 2016-10-26 | 2018-05-03 | Schmidt + Clemens Gmbh + Co. Kg | Tieflochbohrverfahren, werkzeug für eine tieflochbohrmaschine, tieflochbohrmaschine, und schleudergussrohr |
US11612967B2 (en) | 2016-11-09 | 2023-03-28 | Kubota Corporation | Alloy for overlay welding and reaction tube |
US11059134B2 (en) | 2016-11-09 | 2021-07-13 | Kubota Corporation | Alloy for overlay welding and reaction tube |
DE102017003409A1 (de) | 2017-04-07 | 2018-10-11 | Schmidt + Clemens Gmbh + Co. Kg | Rohr und Vorrichtung zum thermischen Spalten von Kohlenwasserstoffen |
US11220635B2 (en) | 2017-04-07 | 2022-01-11 | Schmidt + Clemens Gmbh + Co. Kg | Pipe and device for thermally cleaving hydrocarbons |
WO2018185167A1 (de) | 2017-04-07 | 2018-10-11 | Schmidt + Clemens Gmbh + Co. Kg | Rohr und vorrichtung zum thermischen spalten von kohlenwasserstoffen |
EP3384981A1 (de) | 2017-04-07 | 2018-10-10 | Schmidt + Clemens GmbH & Co. KG | Rohr und vorrichtung zum thermischen spalten von kohlenwasserstoffen |
DE102017003409B4 (de) | 2017-04-07 | 2023-08-10 | Schmidt + Clemens Gmbh + Co. Kg | Rohr und Vorrichtung zum thermischen Spalten von Kohlenwasserstoffen |
US11408057B2 (en) | 2018-06-07 | 2022-08-09 | Manoir Pitres | Austenitic alloy with high aluminum content and associated design process |
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