EP2350329A1 - Nickel-chrom-legierung - Google Patents
Nickel-chrom-legierungInfo
- Publication number
- EP2350329A1 EP2350329A1 EP09744619A EP09744619A EP2350329A1 EP 2350329 A1 EP2350329 A1 EP 2350329A1 EP 09744619 A EP09744619 A EP 09744619A EP 09744619 A EP09744619 A EP 09744619A EP 2350329 A1 EP2350329 A1 EP 2350329A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- nickel
- chromium
- aluminum
- iron
- Prior art date
- 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.)
- Granted
Links
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 title claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 37
- 239000000956 alloy Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005336 cracking Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000002407 reforming Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 230000003750 conditioning effect Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 150000002835 noble gases Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 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 abstract description 5
- 239000010410 layer Substances 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000000571 coke Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 150000001247 metal acetylides Chemical class 0.000 description 7
- 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
- 238000002474 experimental method Methods 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
- 238000001000 micrograph Methods 0.000 description 4
- -1 C 6 carbides Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 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
- 239000006104 solid solution Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000243 solution 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
- 238000003723 Smelting Methods 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
- 238000002679 ablation Methods 0.000 description 1
- 238000005275 alloying Methods 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
- 230000008901 benefit Effects 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
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001143 conditioned effect Effects 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 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
- 238000002203 pretreatment Methods 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
- 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
- 230000008646 thermal stress Effects 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
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.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
PL17207317T PL3330390T3 (pl) | 2008-10-13 | 2009-10-13 | Stop niklowo-chromowy |
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 |
---|---|---|---|
EP17207317.3A Division EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP19172613.2A Division EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2350329A1 true EP2350329A1 (de) | 2011-08-03 |
EP2350329B1 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 |
EP17207317.3A Active EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP09744619.9A Active EP2350329B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19172613.2A Withdrawn EP3550045A1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
EP17207317.3A Active EP3330390B1 (de) | 2008-10-13 | 2009-10-13 | Nickel-chrom-legierung |
Country Status (20)
Country | Link |
---|---|
US (2) | US9249482B2 (de) |
EP (3) | EP3550045A1 (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) | HUE037289T2 (de) |
IL (1) | IL212098A (de) |
MX (1) | MX2011003923A (de) |
MY (1) | MY160131A (de) |
PL (2) | PL3330390T3 (de) |
PT (2) | PT2350329T (de) |
TR (1) | TR201802979T4 (de) |
UA (1) | UA109631C2 (de) |
WO (1) | WO2010043375A1 (de) |
ZA (1) | ZA201102259B (de) |
Cited By (1)
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WO2019034845A1 (en) | 2017-08-15 | 2019-02-21 | Paralloy Limited | ALLOY RESISTANT TO OXIDATION |
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2008
- 2008-10-13 DE DE102008051014A patent/DE102008051014A1/de not_active Withdrawn
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2009
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- 2009-10-13 HU HUE09744619A patent/HUE037289T2/hu unknown
- 2009-10-13 KR KR1020197035927A patent/KR102080674B1/ko active IP Right Grant
- 2009-10-13 CA CA2740160A patent/CA2740160C/en active Active
- 2009-10-13 MY MYPI2011001580A patent/MY160131A/en unknown
- 2009-10-13 ES ES09744619.9T patent/ES2661333T3/es active Active
- 2009-10-13 EP EP19172613.2A patent/EP3550045A1/de not_active Withdrawn
- 2009-10-13 JP JP2011531390A patent/JP2012505314A/ja active Pending
- 2009-10-13 WO PCT/EP2009/007345 patent/WO2010043375A1/de active Application Filing
- 2009-10-13 HU HUE17207317A patent/HUE046718T2/hu unknown
- 2009-10-13 MX MX2011003923A patent/MX2011003923A/es active IP Right Grant
- 2009-10-13 US US13/124,016 patent/US9249482B2/en active Active
- 2009-10-13 PT PT97446199T patent/PT2350329T/pt unknown
- 2009-10-13 BR BR122016030244A patent/BR122016030244A2/pt not_active Application Discontinuation
- 2009-10-13 KR KR1020197028227A patent/KR102064375B1/ko active IP Right Grant
- 2009-10-13 PL PL17207317T patent/PL3330390T3/pl unknown
- 2009-10-13 EP EP17207317.3A patent/EP3330390B1/de active Active
- 2009-10-13 PT PT172073173T patent/PT3330390T/pt unknown
- 2009-10-13 PL PL09744619T patent/PL2350329T3/pl unknown
- 2009-10-13 BR BRPI0920279-0A patent/BRPI0920279B1/pt active IP Right Grant
- 2009-10-13 UA UAA201106001A patent/UA109631C2/ru unknown
- 2009-10-13 EA EA201170560A patent/EA020052B1/ru not_active IP Right Cessation
- 2009-10-13 KR KR1020117008378A patent/KR101738390B1/ko active IP Right Grant
- 2009-10-13 ES ES17207317T patent/ES2747898T3/es active Active
- 2009-10-13 EP EP09744619.9A patent/EP2350329B1/de active Active
- 2009-10-13 CN CN2009801407879A patent/CN102187003B/zh active Active
- 2009-10-13 KR KR1020177013029A patent/KR102029019B1/ko active IP Right Grant
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2011
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- 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
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2015
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2017
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