EP2350329B1 - Nickel-chrom-legierung - Google Patents
Nickel-chrom-legierung Download PDFInfo
- Publication number
- EP2350329B1 EP2350329B1 EP09744619.9A EP09744619A EP2350329B1 EP 2350329 B1 EP2350329 B1 EP 2350329B1 EP 09744619 A EP09744619 A EP 09744619A EP 2350329 B1 EP2350329 B1 EP 2350329B1
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- EP
- European Patent Office
- Prior art keywords
- alloy
- nickel
- chromium
- heating
- furnaces
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910000623 nickel–chromium alloy Inorganic materials 0.000 title claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000005336 cracking Methods 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000002407 reforming Methods 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009749 continuous casting Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 26
- 239000000571 coke Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001247 metal acetylides Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000005255 carburizing Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- -1 chromium carbides Chemical class 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000713 I alloy Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
-
- 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 resistant to both temperature and corrosion and, in particular, have grown on the one hand from the hot product and, on the other hand, from the hot combustion gases of, for example, steam crackers.
- Their coils are subject to external oxidizing aufstickenden combustion gases with temperatures up to 1100 ° 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 risk that diffuses from there the carbon in the pipe material, the carbides in the material increase and 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 as well as a reduction in the strength and toughness of the tubing material.
- German patent specification describes 103 02 989 a nickel-chromium casting alloy 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 proven itself in particular when used as a pipe material, although the practice continues to call for pipe materials with extended life.
- Japanese Laid-Open Publication describes 2004 052 036 a chromium-nickel-iron alloy suitable as a material for high-temperature furnaces with 0.1 to 0.6% carbon, 20 to 40% chromium, 1.5 to 4% aluminum, up to 3% silicon, up to 3% manganese, 0, 5 to 2% niobium, 0.5 to 5% tungsten, 0.01 to 0.5% titanium, 0.01 to 0.5% zirconium, 0.5 to 5% molybdenum and 20 to 65% nickel; Rest iron.
- the invention is therefore directed to a nickel-chromium alloy having improved durability under conditions such as cracking and reforming of hydrocarbons.
- the alloy according to the invention is characterized in particular by its comparatively high contents of chromium and nickel and by a compelling 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 additionally favorable on the weldability, deoxidizes the melt and binds the sulfur stable.
- 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 creep strength by means of solid solution hardening, zirconium through the formation of carbides, especially in conjunction with titanium and tantalum.
- 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 M23C6 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 pipe 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 Strip and strip casting plants, hoods and sleeves for annealing furnaces, parts of large diesel engines and shaped bodies for catalyst fillings.
- the alloy is characterized by a high oxidation and carburization resistance as well as good creep strength and creep resistance.
- the inner surface of cracking or reformer tubes is 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. In such a boring occurs due to the contact pressure to a cold deformation or work hardening of the pipe material 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 adherent aluminum-containing oxide forms a closed protective layer of the tube inner wall, which is largely free of catalytically active centers such as nickel or iron and even after a prolonged cyclic heat stress is still stable.
- This aluminum-containing oxide layer prevents, in contrast to other pipe materials without such a cover layer, the penetration of oxygen into the base material and thus an internal oxidation of the pipe material.
- the cover layer suppresses not only the carburizing of the pipe material, but also corrosion by impurities in the process gas.
- the top layer consists mainly 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 pipes 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 with 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 during the conditioning preferably consists of an extremely weakly oxidizing mixture of water vapor, hydrogen, hydrocarbons and noble gases in an amount such that the oxygen partial pressure of the mixture at a temperature of 600 ° 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, d. H. the separate heating of the resulting cold-formed surface zone is preferably carried out under very weak oxidizing inert gas in several phases each at a rate of 10 to 100 ° C / h initially to 400 to 750 ° C, preferably about 550 ° C at 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 ° C and is ready for operation.
- the tube temperature gradually increases in the cracking operation as a result of the deposition of pyrolytic coke and finally reaches about 1000 ° C or even 1050 ° C on the inner surface.
- the inner layer consisting essentially of Al 2 O 3 and to a small extent of (Al, Cr) 2 O 3 converts from a transition oxide such as ⁇ , ⁇ or ⁇ -Al 2 O 3 into stable ⁇ -aluminum oxide.
- the tube has reached its operating state with its mechanically removed inner layer in a multi-stage, but preferably eintoxicityen method.
- This precursor includes initial heating after abrading the inner surface to holding at 400 to 750 ° C.
- the pipe thus pretreated can then be further processed in situ, for example in another manufacturing facility, starting from its cold state in the manner described above, that is to say in another factory. H. be brought to the operating temperature in the installed state.
- the mentioned separate pretreatment 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.
- nickel alloys in comparison with ten other nickel alloys whose composition is shown in Table I and which are particularly suitable for their contents of carbon (alloys 5 and 6), chromium (alloys 4, 13 and 14), aluminum (alloys 12 , 13), cobalt (alloys 1, 2) and iron (alloys 3, 12, 14, 15), differ from the first five nickel-chromium-iron alloy.
- alloy 9 experiences no internal oxidation even after more than 200 cycles of annealing at 1150 ° C for 45 minutes, whereas the two comparative alloys 12 and 13 show increasing weight loss after only a few cycles as a result of catastrophic oxidation.
- the 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 strength of the nickel alloy 11 is even better in a substantial range than in the case of the two comparative alloys 12 and 13.
- the exception here is the alloy 15, which is not covered by the invention because of its low iron content. however, with their much lower oxidation, carburization and coking resistance.
- FIGS. 5 and 6 Examples of the surface condition of the tube interior of furnace tubes with the composition of the alloy 8 are shown in FIGS. 5 and 6.
- the FIGS Figure 6 (Experiment 7 according to Table II) shows the superiority of a surface after a conditioning according to the invention in comparison to the Figure 5 , which relates to a not according to the invention conditioned surface (Table II, Experiment 2).
- FIG. 7 Shown in Figures 7 (Alloy 14) and 8 are shallow areas in cross section.
- the samples were heated to 950 ° C and then subjected to 10 crack cycles of 10 hours each in an atmosphere of water vapor, hydrogen and hydrocarbons. After each cycle, the sample tubes were burned out for one hour to remove the coke deposits.
- the micrograph of the image 7 in the form of the dark areas shows the large-area and thus bulky 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, which is virtually none 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.
- sample 9 does not have a carbon nanotube after the same tenfold cyclic cracking and subsequent aging in a coking atmosphere which is due to a substantially continuous, catalytically inert, aluminum-containing oxide layer.
- Figure 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 is particularly evident in the course of the aluminum concentration over the depth of the edge zone after ten cracking phases with respective removal of the coke deposits by burnout in an intermediate phase compared to the diagrams in Figs 9 near the near surface due to the local failure of the protective overcoat and then onset of strong internal aluminum oxidation of the material is depleted of aluminum, the aluminum concentration in the diagram of the image 10 moves approximately at the starting level of the casting material. This clearly shows the importance of a continuous, dense and in particular firmly adhering inner aluminum-containing oxide layer in the tubes according to the invention.
- 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 were heated to 950 ° C. under steam and then subjected to cracking at this temperature three times each for 72 hours; they were then subjected to burnout at 900 ° C for four hours each.
- Image 12 shows the closed aluminum-containing oxide layer after the three crack cycles and beyond how the aluminum-containing oxide layer covers the material itself over chromium carbides in the surface. It can be seen that chromium carbides present on the surface are completely covered by the aluminum-containing oxide layer.
- the inventive nickel-chromium-iron alloy is characterized, for example, as a pipe material after removal of the inner surface under mechanical pressure and a subsequent multi-stage in situ heat treatment for conditioning the inner surface by a high oxidation, corrosion and especially high Creep rupture 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)
- Hydrogen, Water And Hydrids (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL17207317T PL3330390T3 (pl) | 2008-10-13 | 2009-10-13 | Stop niklowo-chromowy |
EP17207317.3A EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP19172613.2A EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
PL09744619T PL2350329T3 (pl) | 2008-10-13 | 2009-10-13 | Stop niklowo-chromowy |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008051014A DE102008051014A1 (de) | 2008-10-13 | 2008-10-13 | Nickel-Chrom-Legierung |
PCT/EP2009/007345 WO2010043375A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19172613.2A Division EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP17207317.3A Division EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2350329A1 EP2350329A1 (de) | 2011-08-03 |
EP2350329B1 true EP2350329B1 (de) | 2017-12-20 |
Family
ID=41491665
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19172613.2A Withdrawn EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP09744619.9A Active EP2350329B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP17207317.3A Active EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19172613.2A Withdrawn EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17207317.3A Active EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Country Status (20)
Country | Link |
---|---|
US (2) | US9249482B2 (zh) |
EP (3) | EP3550045A1 (zh) |
JP (4) | JP2012505314A (zh) |
KR (4) | KR101738390B1 (zh) |
CN (1) | CN102187003B (zh) |
BR (2) | BR122016030244A2 (zh) |
CA (1) | CA2740160C (zh) |
DE (1) | DE102008051014A1 (zh) |
EA (1) | EA020052B1 (zh) |
ES (2) | ES2747898T3 (zh) |
HU (2) | HUE037289T2 (zh) |
IL (1) | IL212098A (zh) |
MX (1) | MX2011003923A (zh) |
MY (1) | MY160131A (zh) |
PL (2) | PL3330390T3 (zh) |
PT (2) | PT3330390T (zh) |
TR (1) | TR201802979T4 (zh) |
UA (1) | UA109631C2 (zh) |
WO (1) | WO2010043375A1 (zh) |
ZA (1) | ZA201102259B (zh) |
Families Citing this family (50)
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DE102012011162B4 (de) * | 2012-06-05 | 2014-05-22 | Outokumpu Vdm Gmbh | Nickel-Chrom-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
US9540714B2 (en) | 2013-03-15 | 2017-01-10 | Ut-Battelle, Llc | High strength alloys for high temperature service in liquid-salt cooled energy systems |
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US10017842B2 (en) | 2013-08-05 | 2018-07-10 | Ut-Battelle, Llc | Creep-resistant, cobalt-containing alloys for high temperature, liquid-salt heat exchanger systems |
US9435011B2 (en) | 2013-08-08 | 2016-09-06 | Ut-Battelle, Llc | Creep-resistant, cobalt-free alloys for high temperature, liquid-salt heat exchanger systems |
CN105723009B (zh) * | 2013-11-12 | 2017-08-18 | 新日铁住金株式会社 | Ni‑Cr合金材料以及使用其的油井用无缝管 |
US9683280B2 (en) | 2014-01-10 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
DE102014001329B4 (de) | 2014-02-04 | 2016-04-28 | VDM Metals GmbH | Verwendung einer aushärtenden Nickel-Chrom-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
DE102014001330B4 (de) | 2014-02-04 | 2016-05-12 | VDM Metals GmbH | Aushärtende Nickel-Chrom-Kobalt-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
US11674212B2 (en) | 2014-03-28 | 2023-06-13 | Kubota Corporation | Cast product having alumina barrier layer |
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CA3058824A1 (en) | 2017-04-07 | 2018-10-11 | Schmidt + Clemens Gmbh + Co. Kg | Pipe and device for thermally cleaving hydrocarbons |
GB201713066D0 (en) | 2017-08-15 | 2017-09-27 | Paralloy Ltd | Oxidation resistant alloy |
US10456768B2 (en) | 2017-09-12 | 2019-10-29 | Exxonmobil Chemical Patents Inc. | Aluminum oxide forming heat transfer tube for thermal cracking |
JP6422608B1 (ja) * | 2017-11-06 | 2018-11-14 | 株式会社クボタ | 耐熱合金及び反応管 |
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KR101998979B1 (ko) * | 2017-12-07 | 2019-07-10 | 주식회사 포스코 | 고온변형 저항성 및 균열 저항성이 우수한 복사관용 Cr-Ni계 합금 및 그 제조방법 |
JP7016283B2 (ja) * | 2018-04-25 | 2022-02-04 | 株式会社クボタ | 耐高温腐食性を有する耐熱合金、溶接用粉末及び外周面に肉盛溶接層を具える配管 |
FR3082209B1 (fr) | 2018-06-07 | 2020-08-07 | Manoir Pitres | Alliage austenitique avec haute teneur en aluminium et procede de conception associe |
CN109112327B (zh) * | 2018-11-08 | 2019-09-03 | 青岛新力通工业有限责任公司 | 一种抗氧化耐热合金及制备方法 |
CN113227328A (zh) * | 2018-12-20 | 2021-08-06 | 埃克森美孚化学专利公司 | 用于热裂化反应器的耐侵蚀合金 |
CN110016602B (zh) * | 2019-04-22 | 2020-06-02 | 陕西科技大学 | 一种Laves相Cr2Nb基高温合金 |
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JP7560732B2 (ja) | 2020-02-14 | 2024-10-03 | 日本製鉄株式会社 | オーステナイト系ステンレス鋼材 |
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CN111850348B (zh) * | 2020-07-30 | 2021-11-09 | 北京北冶功能材料有限公司 | 一种高强高韧镍基高温合金箔材及其制备方法 |
CN112853155A (zh) * | 2021-01-08 | 2021-05-28 | 烟台玛努尔高温合金有限公司 | 具有优异高温耐腐蚀性和抗蠕变性的高铝奥氏体合金 |
US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
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CN113073234B (zh) * | 2021-03-23 | 2022-05-24 | 成都先进金属材料产业技术研究院股份有限公司 | 镍铬系高电阻电热合金及其制备方法 |
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-
2008
- 2008-10-13 DE DE102008051014A patent/DE102008051014A1/de not_active Withdrawn
-
2009
- 2009-10-13 KR KR1020117008378A patent/KR101738390B1/ko active IP Right Grant
- 2009-10-13 PL PL17207317T patent/PL3330390T3/pl unknown
- 2009-10-13 EP EP19172613.2A patent/EP3550045A1/de not_active Withdrawn
- 2009-10-13 PL PL09744619T patent/PL2350329T3/pl unknown
- 2009-10-13 MY MYPI2011001580A patent/MY160131A/en unknown
- 2009-10-13 UA UAA201106001A patent/UA109631C2/ru unknown
- 2009-10-13 EP EP09744619.9A patent/EP2350329B1/de active Active
- 2009-10-13 PT PT172073173T patent/PT3330390T/pt unknown
- 2009-10-13 BR BR122016030244A patent/BR122016030244A2/pt not_active Application Discontinuation
- 2009-10-13 PT PT97446199T patent/PT2350329T/pt unknown
- 2009-10-13 HU HUE09744619A patent/HUE037289T2/hu unknown
- 2009-10-13 WO PCT/EP2009/007345 patent/WO2010043375A1/de active Application Filing
- 2009-10-13 EA EA201170560A patent/EA020052B1/ru not_active IP Right Cessation
- 2009-10-13 JP JP2011531390A patent/JP2012505314A/ja active Pending
- 2009-10-13 US US13/124,016 patent/US9249482B2/en active Active
- 2009-10-13 BR BRPI0920279-0A patent/BRPI0920279B1/pt active IP Right Grant
- 2009-10-13 ES ES17207317T patent/ES2747898T3/es active Active
- 2009-10-13 MX MX2011003923A patent/MX2011003923A/es active IP Right Grant
- 2009-10-13 KR KR1020197028227A patent/KR102064375B1/ko active IP Right Grant
- 2009-10-13 ES ES09744619.9T patent/ES2661333T3/es active Active
- 2009-10-13 TR TR2018/02979T patent/TR201802979T4/tr unknown
- 2009-10-13 CN CN2009801407879A patent/CN102187003B/zh active Active
- 2009-10-13 EP EP17207317.3A patent/EP3330390B1/de active Active
- 2009-10-13 CA CA2740160A patent/CA2740160C/en active Active
- 2009-10-13 KR KR1020177013029A patent/KR102029019B1/ko active IP Right Grant
- 2009-10-13 HU HUE17207317A patent/HUE046718T2/hu unknown
- 2009-10-13 KR KR1020197035927A patent/KR102080674B1/ko active IP Right Grant
-
2011
- 2011-03-25 ZA ZA2011/02259A patent/ZA201102259B/en unknown
- 2011-04-03 IL IL212098A patent/IL212098A/en active IP Right Grant
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2014
- 2014-06-17 JP JP2014124723A patent/JP2014185397A/ja active Pending
-
2015
- 2015-12-21 US US14/976,389 patent/US10053756B2/en active Active
-
2017
- 2017-03-13 JP JP2017047576A patent/JP6320590B2/ja active Active
-
2018
- 2018-04-02 JP JP2018070880A patent/JP6486532B2/ja active Active
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