EP2397573B1 - Method for producing metal tube - Google Patents
Method for producing metal tube Download PDFInfo
- Publication number
- EP2397573B1 EP2397573B1 EP10741311.4A EP10741311A EP2397573B1 EP 2397573 B1 EP2397573 B1 EP 2397573B1 EP 10741311 A EP10741311 A EP 10741311A EP 2397573 B1 EP2397573 B1 EP 2397573B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- metal pipe
- pipe
- content
- oxide scale
- 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.)
- Not-in-force
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 104
- 239000002184 metal Substances 0.000 title claims description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 description 61
- 239000007789 gas Substances 0.000 description 25
- 238000005422 blasting Methods 0.000 description 23
- 238000004939 coking Methods 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 20
- 239000000314 lubricant Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005255 carburizing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 239000001273 butane Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910001208 Crucible steel Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005480 shot peening Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 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
- 239000011261 inert gas Substances 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
- B21C37/15—Making tubes of special shape; Making tube fittings
- B21C37/20—Making helical or similar guides in or on tubes without removing material, e.g. by drawing same over mandrels, by pushing same through dies ; Making tubes with angled walls, ribbed tubes and tubes with decorated walls
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
- C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
-
- 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
- C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 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
- C22C19/053—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%
-
- 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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
Definitions
- the present invention relates to a method for manufacturing a metal pipe having a scale layer at least on the inner surface thereof. More particularly, the present invention relates to a method for manufacturing a metal pipe excellent in high-temperature strength and corrosion resistance.
- the metal pipe obtained by the present invention is suitably used as a pipe used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like, such as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, and a heat exchanger pipe in an oil refining plant, a petrochemical plant, and the like.
- a metal pipe containing 20 to 35 mass % of Cr and 20 to 70 mass % of Ni has been used as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, a heat exchanger pipe, and the like used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like in, for example, an oil refining plant or a petrochemical plantmass %mass %.
- This metal pipe is excellent in high-temperature strength and corrosion resistance.
- an oxide scale layer consisting mainly of Cr is preferably formed on the inner surface of the metal pipe in order to prevent carburization.
- the oxide scale layer consisting mainly of Cr is highly dense, and has an effect of shielding the intrusion of carbon into the metal pipe.
- the oxide scale layer consisting mainly of Cr has a weak catalytic action against coking (deposit of carbon). Therefore, the oxide scale layer consisting mainly of Cr also has an effect of restraining coking on the surface of metal pipe. As a result, the thermal conductivity to a fluid introduced into the metal pipe can be kept for a long period of time.
- Patent Document 1 discloses a method in which when a stainless steel pipe containing 12 to 20 mass % of Cr and 40 mass % or less of Ni is used in a high temperature and pressure water environment, the steel pipe is subjected to heat treatment of being heated to 800 to 1100°C under an inert gas atmosphere containing 0.01 to 0.5 vol% of oxygen and being held at that temperature for 2 to 20 minutes to form a scale layer on the surface of the steel pipe in order to prevent the Ni release from the steel pipe.
- Patent Document 2 discloses an invention in which an austenitic stainless steel containing 14 mass % or less of Cr is heat treated at a temperature not lower than 1100°C while the CO concentration in a barrel furnace is controlled to at least 150 ppm to prevent unevenness of scale caused by abnormal oxidation of the steel surface.
- Patent Document 3 discloses an invention relating to a stainless steel used in a carburizing gas atmosphere, the stainless steel having an oxide scale layer consisting mainly of Cr, in which the Cr concentration in a Cr depleted zone is at least 10% by mass, on the surface of a base metal containing 20 to 55 mass % of Cr, and further having an oxide scale layer consisting mainly of Cr, in which the Cr content is at least 50% by mass, on the outside thereof.
- Patent Document 4 relates to a method for manufacturing an ethylene pyrolytic furnace pipe excellent in coking resistance, and discloses an invention in which a pipe containing 15 to 30 mass % of Cr and 15 to 50 mass % of Ni is subjected to cold working of at least 50 ⁇ m depth from the surface, and then the pipe is heated to a temperature not lower than 1100°C in an atmosphere containing less than 5 vol% of oxygen and at least 20 vol% of nitrogen.
- the stainless steel having the oxide scale layer as described in Patent Document 3 is excellent in carburization resistance and coking resistance. However, in actual manufacturing, it is difficult to uniformly form the oxide scale layer consisting mainly of Cr over the entire inner surface, of pipe.
- Patent Document 4 describes that a fine-grained layer of not less than No. 7 in the austenitic crystal grain size can be created to a depth of at least 30 ⁇ m from the surface with cold working and nitrogen permeating heat treatment, so that the stability of Cr 2 O 3 oxide film produced during the use under an actual operation condition of 750 to 1100°C can be improved.
- the oxide scale produced in the nitrogen permeating heat treatment is removed, and a stable Cr 2 O 3 oxide film is formed on the fine-grained layer in the actual operation.
- the formation of oxide film during the actual operation requires a long period of time. In this method, therefore, carburization or coking may occur before the stable oxide film is formed.
- the present invention has been made to solve the above problems with prior arts, and accordingly an objective thereof is to provide a method for manufacturing a metal pipe having excellent resistance to carburization or coking caused by a carburizing gas by forming a uniform oxide scale layer consisting mainly of Cr on the inner surface of metal pipe.
- the present inventors earnestly conducted studies on the method for uniformly forming the oxide scale layer consisting mainly of Cr having carburization resistance and coking resistance over the entire inner surface of metal pipe, and resultantly obtained the findings concerning the cause for the formation of nonuniform scale and the method for preventing the formation of nonuniform scale, as described below.
- the present invention was completed on the basis of the above-described findings, and the gist thereof is methods for manufacturing a metal pipe given in the items (1) to (4) listed below.
- a metal pipe having an oxide scale layer consisting mainly of Cr formed uniformly on the inner surface of the metal pipe can be manufactured.
- the metal pipe obtained by the manufacturing method of the present invention is excellent in carburization resistance and coking resistance in a carburizing gas environment.
- the present invention provides a method for manufacturing a metal pipe according to claim 1, wherein the inner surface of a metal pipe having a predetermined chemical composition is subjected to mechanical treatment; the metal pipe is subjected to heat treatment such as to be held in a temperature range of 1050 to 1270°C for 0.5 to 60 minutes; and thereby an oxide scale layer consisting mainly of Cr is formed on at least the inner surface of the metal pipe.
- the chemical composition of the metal pipe obtained by the manufacturing method of the present invention, and the mechanical treatment and heat treatment to which the metal pipe is subjected are described.
- “%" relating to the content of each element means “mass %".
- the metal pipe obtained by the manufacturing method of the present invention must contain 20 to 55% of Cr and 20 to 70% of Ni.
- the upper limit of Cr content is set to 55%. To ensure the workability and to prevent the structural stability from deteriorating, the upper limit of Cr content is preferably set to 35%. The further preferable range of Cr content is 22 to 33%.
- Ni is an element necessary for obtaining a stable austenitic structure. Ni should be contained in an appropriate amount depending on the Cr content. Ni has an effect of reducing the intrusion rate of carbon into the metal material. This effect is achieved in the case where the Ni content is set to at least 20%. However, even if Ni is added excessively, the effect saturates, and the manufacturing cost is increased. Excessive Ni makes the manufacture of pipe difficult. Therefore, the Ni content is set to 20 to 70%. The lower limit of Ni content is preferably set to 23%, and the upper limit thereof is preferably set to 60%, further preferably 50%.
- the starting material for a metal pipe for manufacturing ethylene preferably contains Cr: 20 to 35% and Ni: 20 to 60%.
- the metal pipe obtained by the manufacturing method of the present invention has the above-described chemical composition, and other components are not limited.
- the metal pipe preferably has a chemical composition consisting of C: 0.01 to 0.6%, Si: 0.1 to 5%, Mn: 0.1 to 10%, P: 0.08% or less, S: 0.05% or less, Cr: 20 to 55%, Ni: 20 to 70%, N: 0.001 to 0.25%, O (oxygen): 0.02% or less, the balance being Fe and impurities.
- the reasons for restricting the content of each element are described.
- the impurities are components that mixedly enter from raw ore, scrap, and the like when the metal pipe is manufactured on an industrial basis, and are permitted as far as the content range does not adversely affect the present invention.
- C Carbon is an element effective in ensuring the high-temperature strength. This effect is remarkable when at least 0.01% of C is contained. If the C content exceeds 0.6%, the toughness may be deteriorated extremely. Therefore, the C content is preferably set to 0.01 to 0.6%.
- the lower limit of C content is further preferably set to 0.02%, and the upper limit thereof is further preferably set to 0.45%, still further preferably 0.3%.
- Si (Silicon) has an effect of assisting the uniform formation of the oxide scale layer consisting mainly of Cr because the affinity of Si for oxygen is high. This effect is remarkable when at least 0.1% of Si is contained. However, if the Si content exceeds 5%, the weldability is deteriorated, and the micro-structure may become unstable. Therefore, the Si content is preferably set to 0.1 to 5%.
- the upper limit of Si content is preferably set to 3%, further preferably 2%, and the lower limit thereof is preferably set to 0.3%.
- Mn Manganese
- Mn is an element effective for deoxidation and in improving the workability. Also, because Mn is an austenite producing element, some of Ni can be replaced with Mn. To achieve these effects, at least 0.1 % of Mn is preferably contained. However, if Mn is contained excessively, the formation of the oxide scale layer consisting mainly of Cr may be hindered. Therefore, the Mn content is preferably set to 0.1 to 10%. The upper limit of Mn content is preferably set to 5%, further preferably 2%.
- P (Phosphorus) and S (Sulfur) are preferably reduced in amount as far as possible because these elements segregate at the crystal grain boundary and deteriorate the hot workability.
- the P content is preferably 0.08% or less, and the S content is preferably 0.05% or less.
- the P content is further preferably set to 0.05% or less, and the S content is further preferably set to 0.03% or less.
- the P content is still further preferably set to 0.04% or less, and the S content is still further preferably set to 0.015% or less.
- N (Nitrogen) is an element effective in improving the high-temperature strength. This effect is remarkable when at least 0.001% of N is contained. However, the excessive addition of N may hinder the workability greatly. Therefore, the N content is preferably set to 0.001 to 0.25%. The upper limit of N content is preferably set to 0.2%.
- O Oxygen
- Oxygen is an element existing as an impurity. If the O content exceeds 0.02%, the oxide-base inclusions in the metal material precipitate in large amounts, which decrease the workability, so that the inclusions are a cause for the surface defects of pipe. Therefore, the O content is preferably set to 0.02% or less.
- the above-described metal pipe may further contain one or more elements selected from the elements given in the items (a) to (g) listed below.
- Cu is an element for stabilizing the austenitic phase.
- Cu is also an element effective in improving the high-temperature strength. Therefore, Cu may be contained in the above-described metal pipe. However, if the Cu content is excessive, the hot workability may be decreased. Therefore, if Cu is contained, the content thereof is preferably set to 5% or less. The upper limit of the Cu content is further preferably set to 3%. The above-described effects are remarkable when 0.1% or less of Cu is contained.
- Co is an element for stabilizing the austenitic phase. If Co is contained, some of Ni can be replaced with Co. Therefore, Co may be contained in the above-described metal pipe. However, if the Co content is excessive, the hot workability may be decreased. Therefore, if Co is contained, the content thereof is preferably set to 5% or less. The upper limit of the Co content is further preferably set to 3%. The above-described effect is remarkable when 0.1 % or less of Co is contained.
- Mo Mo
- W Tin
- Ta tantalum
- Mo Mo
- W Tin
- Ta tantalum
- Mo Mo
- the Mo content is preferably set to 3% or less
- the W and Ta contents each are preferably set to 6% or less.
- the upper limit of each of these elements is further preferably set to 2.5%, still further preferably 2% or less.
- the upper limit of the total amount is preferably set to 10%.
- Ti (Titanium) and Nb (Niobium) have great effects of improving the high-temperature strength, ductility, and toughness even if minute amounts of them are contained. Therefore, one or two selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the workability and weldability may be deteriorated. Therefore, if one or two of these elements are contained, the Ti content is preferably set to 1% or less, and the Nb content is preferably set to 2% or less. For each of these elements, the above-described effects are remarkable when at least 0.01 % of each of these elements is contained. When these elements are contained compositely, the upper limit of the total amount is preferably set to 2%.
- B (Boron), Zr (Zirconium) and Hf (Hafnium) are elements effective in strengthening the grain boundary and improving the hot workability and high-temperature strength. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the weldability may be deteriorated. Therefore, if at least one of these elements is contained, the B and Zr contents each are preferably set to 0.1% or less, and the Hf content is preferably set to 0.5% or less. For each of these elements, the above-described effects are remarkable when at least 0.001% of each of these elements is contained. When these elements are contained compositely, the upper limit of the total amount is preferably set to 0.3%.
- Mg (Magnesium), Ca (Calcium) and Al (Aluminum) are elements effective in improving the hot workability. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the weldability may be deteriorated. Therefore, if at least one of these elements is contained, the Mg content is preferably set to 0.1% or less, the Ca content is preferably set to 0.1% or less, and the Al content is preferably set to 1% or less.
- the upper limits of the Mg content and the Ca content each are further preferably set to 0.05%, and the upper limit of the Al content is further preferably set to 0.6%.
- the above-described effect is remarkable when at least 0.001% of each of Mg and Ca is contained and when at least 0.01% of A1 is contained.
- the lower limits of the Mg content and the Ca content each are preferably set to 0.002%.
- the upper limit of the total amount is preferably set to 0.5%.
- Y (Yttrium) and Ln (Lanthanide) group elements are elements effective in improving the oxidation resistance. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the workability is deteriorated. Therefore, if at least one of these elements is contained, the content of each element is preferably set to 0.15% or less. The above-described effect is remarkable when at least 0.0005% of each of these elements is contained.
- the upper limit of the content of each of these elements is further preferably set to 0.10%. When these elements are contained compositely, the upper limit of the total amount is preferably set to 0.15%.
- the Ln group elements are elements of La, which is element number 57, through Lu, which is element number 71. Among the Ln group elements, at least one of La, Ce and Nd is preferably used.
- a lubricant is used to reduce the friction between the metal pipe and a working tool.
- the lubricant is usually removed by degreasing and cleaning after working.
- some of the lubricant remains on the inner surface of pipe.
- the lubricant remaining on the surface of the metal pipe hinders the formation of the oxide scale layer consisting mainly of Cr.
- mechanical treatment is performed to remove the remaining lubricant.
- the oxide scale produced at the time of hot pipe-making, dirt, and the like are adhered and remain on the surface of the metal pipe. Such remainder is preferably removed because it hinders the uniform formation of the oxide scale layer consisting mainly of Cr.
- the mechanical treatment is treatment for enhancing the cleanliness of the inner surface of the metal pipe by physically removing deposits such as the lubricant remaining on the surface of the metal pipe, dirt, and oxide scale.
- the mechanical treatment includes, for example, blasting treatment, grinding treatment (or friction treatment) for removing the deposits by bringing an abrasive into direct contact with the inner surface of metal pipe and rubbing the inner surface thereof with the abrasive, and a process for removing the deposits by spraying high-pressure water without the use of abrasive.
- blasting treatment for example, there are available air-blasting in which blast media are propelled by compressed air, sandblasting (one kind of air-blasting) in which sand is used as the blast media, shotblasting in which blast media are propelled by the centrifugal force of an impeller made of an abrasion-resistant alloy, shotpeening (one kind of shotblasting) mainly used for giving strain to the metal surface, wet blasting, and the like.
- shots on the surface can be removed simultaneously with the giving of strain.
- Wet blasting in which blast media are propelled together with high-pressure water can also be applied.
- a nonmetal such as silica sand (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), boron nitride (BN), or silicon carbide (SiC), a mixture of these nonmetals or an abrasive containing these nonmetals as principal components is suitably used.
- an abrasive consisting of a metal such as cast steel, stainless steel, metallic glass (amorphous), or Cr may be used.
- a nonwoven fabric or the like to which the abrasive is stuck may also be used.
- the shape of the abrasive is not limited, and the abrasive can take any shape such as a granular shape, a grit shape, or a powder shape.
- the size of the abrasive is not limited. However, in the case where the surface roughness is restrained to enhance the coking resistance, the average grain size (the average of the major axis and the minor axis) is preferably 300 ⁇ m or less, further preferably 150 ⁇ m or less.
- the abrasive may be shot blasted from one end or both ends of the metal pipe, or may be shot blasted while a blasting nozzle is inserted into the metal pipe and is moved in the pipe.
- the abrasive or the nonwoven fabric to which the abrasive is stuck may be brought into direct contact with the inner surface of metal pipe in a state of being dry or being wetted by a liquid and may be moved while rubbing the inner surface of metal pipe.
- the metal pipe is subjected to mechanical treatment, subsequently heat treatment, and thereby an oxide scale layer consisting mainly of Cr is formed on the inner surface of the metal pipe.
- the heat treatment temperature is lower than 1050°C, the oxide scale layer formed on the surface of metal pipe is thin, so that the shielding property against the intrusion of carbon into metal material is insufficient.
- the heat treatment temperature exceeds 1270°C, pores or cracks are occurred in the oxide scale layer, and the denseness is decreased, which results in a decrease in carburization resistance. Therefore, the heat treatment is performed in the temperature range of 1050 to 1270°C.
- the lower limit of heat treatment temperature is preferably 1120°C, further preferably 1160°C.
- the holding time in the above-described temperature range is set to 0.5 to 60 minutes.
- the lower limit of the holding time is preferably set to 2 minutes, further preferably 5 minutes.
- the upper limit of the holding time is preferably set to 30 minutes, further preferably 15 minutes.
- the gas atmosphere in the heat treatment may be any atmosphere in which the oxide scale layer consisting mainly of Cr can be formed.
- the atmosphere of atmospheric gas or a gas obtained by burning a hydrocarbon fuel (LNG, butane, etc.) and air may be used.
- the atmosphere of DX gas, NX gas, RX gas, COG (C gas), or hydrogen gas whose dew point is controlled may be used.
- the atmosphere of a gas obtained by mixing these gases in an arbitrary ratio may also be used.
- Oxide scale layer consisting mainly of Cr
- the oxide scale layer consisting mainly of Cr is very important from the viewpoints of carburization resistance and coking resistance.
- the oxide scale layer containing at least 50% of Cr has a high denseness and is excellent in shielding property against the intrusion of carbon into metal material.
- the oxide scale layer consisting mainly of Cr restrains coking on the surface of metal material because the catalytic action thereof against coking is weak. As a result, the thermal conductivity to a fluid in the pipe is kept for a long period of time. For example, in the case where the metal pipe is used as a decomposition reaction tube, the yield of a reaction product such as olefin is stabilized.
- the Cr content in the oxide scale layer is preferably at least 80%.
- the oxide scale layer having a high Cr content is denser and achieves a great effect of shielding the intrusion of carbon into the metal material.
- the content of element in the oxide scale layer can be measured by EDX. The measurement should be made from the surface of the oxide scale layer. The determination of element is made by the fraction of the detected element excluding C (carbon), O (oxygen), and the like.
- the present invention is especially useful in manufacture of a metal pipe having a rib-shaped protrusion on the inner surface thereof.
- a metal pipe having a rib-shaped protrusion on the inner surface thereof it is thought that the metal pipe is liable to be attacked by carburizing gas, and the oxide scale is liable to peel off.
- a metal pipe having high carburization resistance on the inner surface of the pipe and high repairability of the film can be obtained.
- a pipe having a protrusion on the inner surface thereof, a pipe having fins, and the like are cited as the pipe having the rib-shaped protrusion.
- the protrusion, the fin, and the like may be formed integrally with the pipe itself or may be formed by welding or the like means.
- the present invention is explained below more specifically by way of example.
- the present invention is not limited to the example.
- Metal materials having the chemical composition given in Table 1 were melted by using an electric furnace or a vacuum furnace to form billets.
- the obtained billets were hot forged and cold rolled to produce metal pipes having an outside diameter of 56 mm and a wall thickness of 6 mm.
- the metal pipes of specimen Nos. 1 to 10 were subjected to mechanical treatment of the conditions given in Table 2. For some metal pipes, the mechanical treatment was omitted. Then, the metal pipes were subjected to heat treatment under the conditions given in Table 2 to form oxide scale. Some metal pipes were subjected to alumina blasting as the mechanical treatment, and were not subjected to heat treatment.
- each of the metal pipes was cut at a total of five places at a 2-m pitch along the pipe longitudinal direction to sample ring-shaped specimens each having a width of 50 mm and specimens for observation of oxide scale (20 x 20 mm square), described later. TABLE 1 Specimen No.
- Base metal chemical composition (mass %) C Si Mn P S Cr Ni N O Others 1 0,21 0,36 0,42 0,020 ⁇ 0.001 25,8 24,5 0,04 0,01 0.5Ti 2 0,11 1,67 0,28 0,017 ⁇ 0.001 25,3 38,3 0,02 0,01 1.2Mo, 0.5Ti 3 0,08 0,35 1,20 0,025 ⁇ 0.001 20,7 30,5 0,02 0,01 - 4 0,11 1,85 3,20 0,022 0,001 28,9 42,5 0,05 ⁇ 0.01 1.3Nb, 0.003Ca 5 0,01 0,12 0,15 0,018 ⁇ 0.001 31,2 60,8 0,01 0,01 0.004B, 0.029La 6 0,12 1,54 0,32 0,022 ⁇ 0.001 25,6 38,3 0,02 0,01 1.0W, 1.1Cu, 0.01Y 7 0,11 1,48 0,36 0,020 ⁇ 0.001 24,8 38,5 0,02 0,01 0.004Mg, 0.55Co 8 0,12 1,61 0,34 0,017 ⁇ 0.001 25,7 38,5 0,02
- EDX analysis was made from the surface of the specimen for observation, and the Cr content (mass %) in the oxide scale layer produced on the metal pipe was determined from the average of three measurements.
- carburization and coking tests were conducted by holding the ring-shaped specimen at 1000°C for 300 hours in the gas atmosphere of 15%CH 4 -3%CO 2 -82%H 2 by a volume ratio.
- Concerning the coking resistance the mass of specimen was measured before and after the test to determine the increase amount due to coke deposit, and deposited coke amount per unit area (mg/cm 2 ) was determined.
- Concerning the carburization resistance the amount of C intruding into the base metal was evaluated.
- metal chips were sampled at a 0.5-mm pitch in the depth direction from the surface of the specimen having been tested, and the amount of C (mass %) at a depth of 0.5 to 1.0 mm and the amount of C (mass %) at a depth of 1.0 to 1.5 mm were measured by chemical analysis. After the amount of C (mass %) of base metal before testing was subtracted, the average value of both the amounts of C was defined as the amount of intruding C (mass %) at a depth of 1 mm.
- Table 2 denotes the number of specimens meeting the criteria of the above items (1), (2) and (3) per five specimens. For example, 3/5 denotes that three of five are acceptable.
- the present invention aims at excellent carburization resistance and coking resistance throughout the overall length of the inner surface of metal pipe. Therefore, it was determined that each of the criteria of the present invention is met when all of the five specimens are acceptable.
- a metal pipe having an oxide scale layer consisting mainly of Cr formed uniformly on the inner surface of the metal pipe can be manufactured, so that the metal pipe is excellent in carburization resistance and coking resistance in a carburizing gas environment.
- the metal pipe obtained by the present invention is suitably used especially as a pipe used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like, such as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, and a heat exchanger pipe in an oil refining plant, a petrochemical plant, and the like.
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Description
- The present invention relates to a method for manufacturing a metal pipe having a scale layer at least on the inner surface thereof. More particularly, the present invention relates to a method for manufacturing a metal pipe excellent in high-temperature strength and corrosion resistance. The metal pipe obtained by the present invention is suitably used as a pipe used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like, such as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, and a heat exchanger pipe in an oil refining plant, a petrochemical plant, and the like.
- In recent years, a metal pipe containing 20 to 35 mass % of Cr and 20 to 70 mass % of Ni has been used as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, a heat exchanger pipe, and the like used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like in, for example, an oil refining plant or a petrochemical plantmass %mass %. The reason is that this metal pipe is excellent in high-temperature strength and corrosion resistance.
- The inner surface of the metal pipe is exposed to a carburizing atmosphere. Therefore, an oxide scale layer consisting mainly of Cr is preferably formed on the inner surface of the metal pipe in order to prevent carburization. The oxide scale layer consisting mainly of Cr is highly dense, and has an effect of shielding the intrusion of carbon into the metal pipe. The oxide scale layer consisting mainly of Cr has a weak catalytic action against coking (deposit of carbon). Therefore, the oxide scale layer consisting mainly of Cr also has an effect of restraining coking on the surface of metal pipe. As a result, the thermal conductivity to a fluid introduced into the metal pipe can be kept for a long period of time. Therefore, for example, in the case where such a metal pipe is used as a decomposition reaction tube, the yield of a reaction product such as olefin is stabilized. This oxide scale layer consisting mainly of Cr is also formed in an environment in which the metal pipe is used. However, because carbon intrudes into the metal pipe simultaneously as described above, it is difficult to form the oxide scale layer consisting mainly of Cr uniformly on the inner surface of metal pipe. For this reason, it is effective to form the oxide scale layer consisting mainly of Cr in advance on the inner surface of metal pipe.
- Patent Document 1 discloses a method in which when a stainless steel pipe containing 12 to 20 mass % of Cr and 40 mass % or less of Ni is used in a high temperature and pressure water environment, the steel pipe is subjected to heat treatment of being heated to 800 to 1100°C under an inert gas atmosphere containing 0.01 to 0.5 vol% of oxygen and being held at that temperature for 2 to 20 minutes to form a scale layer on the surface of the steel pipe in order to prevent the Ni release from the steel pipe. Patent Document 2 discloses an invention in which an austenitic stainless steel containing 14 mass % or less of Cr is heat treated at a temperature not lower than 1100°C while the CO concentration in a barrel furnace is controlled to at least 150 ppm to prevent unevenness of scale caused by abnormal oxidation of the steel surface.
- Patent Document 3 discloses an invention relating to a stainless steel used in a carburizing gas atmosphere, the stainless steel having an oxide scale layer consisting mainly of Cr, in which the Cr concentration in a Cr depleted zone is at least 10% by mass, on the surface of a base metal containing 20 to 55 mass % of Cr, and further having an oxide scale layer consisting mainly of Cr, in which the Cr content is at least 50% by mass, on the outside thereof.
- Patent Document 4 relates to a method for manufacturing an ethylene pyrolytic furnace pipe excellent in coking resistance, and discloses an invention in which a pipe containing 15 to 30 mass % of Cr and 15 to 50 mass % of Ni is subjected to cold working of at least 50 µm depth from the surface, and then the pipe is heated to a temperature not lower than 1100°C in an atmosphere containing less than 5 vol% of oxygen and at least 20 vol% of nitrogen.
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- [Patent Document 1]:
JP2-47249A - [Patent Document 2]:
JP3-197617A - [Patent Document 3]:
JP2005-48284A - [Patent Document 4]:
JP2-263895A - In the inventions described in Patent Documents 1 and 2, because the Cr content is as low as 20 mass % or less, it is difficult to form the oxide scale layer consisting mainly of Cr.
- The stainless steel having the oxide scale layer as described in Patent Document 3 is excellent in carburization resistance and coking resistance. However, in actual manufacturing, it is difficult to uniformly form the oxide scale layer consisting mainly of Cr over the entire inner surface, of pipe.
- The invention described in Patent Document 4 describes that a fine-grained layer of not less than No. 7 in the austenitic crystal grain size can be created to a depth of at least 30 µm from the surface with cold working and nitrogen permeating heat treatment, so that the stability of Cr2O3 oxide film produced during the use under an actual operation condition of 750 to 1100°C can be improved. In this method, the oxide scale produced in the nitrogen permeating heat treatment is removed, and a stable Cr2O3 oxide film is formed on the fine-grained layer in the actual operation. However, the formation of oxide film during the actual operation requires a long period of time. In this method, therefore, carburization or coking may occur before the stable oxide film is formed.
- The present invention has been made to solve the above problems with prior arts, and accordingly an objective thereof is to provide a method for manufacturing a metal pipe having excellent resistance to carburization or coking caused by a carburizing gas by forming a uniform oxide scale layer consisting mainly of Cr on the inner surface of metal pipe.
- The present inventors earnestly conducted studies on the method for uniformly forming the oxide scale layer consisting mainly of Cr having carburization resistance and coking resistance over the entire inner surface of metal pipe, and resultantly obtained the findings concerning the cause for the formation of nonuniform scale and the method for preventing the formation of nonuniform scale, as described below.
- (A) Various studies were carried out on the oxide scale layer formed on the inner surface of metal pipe, such as observation using an optical microscope and a scanning electron microscope (SEM), and quantitative analysis of elements using energy dispersive X-ray spectrometry (EDX). As the result, on the surface of nonuniform scale, either one or both of alkali metal and alkaline earth metal were detected.
- (B) According to the results of studies by the present inventors, it was revealed that these elements are derived from a lubricant used at the time of cold working, and the lubricant remaining on the surface of metal pipe is a cause that hinders the formation of the oxide scale layer consisting mainly of Cr.
- (C) After cold working, an attempt was made to remove the lubricant sticking to the inner surface of pipe by carrying out degreasing, cleaning, and the like method. With these methods, however, in some cases, the lubricant could not be removed sufficiently throughout the overall length of metal pipe. Accordingly, various methods were tested for removing the lubricant. As the result, it was found that by subjecting the inner surface of metal pipe to mechanical treatment such as blasting, the lubricant on the inner surface of metal pipe can be removed uniformly throughout the overall length of metal pipe.
- The present invention was completed on the basis of the above-described findings, and the gist thereof is methods for manufacturing a metal pipe given in the items (1) to (4) listed below.
- (1) A method for manufacturing a metal pipe according to claim 1.
- (2) The method for manufacturing a metal pipe according to the above item (1), wherein the metal pipe has a chemical composition consisting of, by mass percent, C: 0.01 to 0.6%, Si: 0.1 to 5%, Mn: 0.1 to 10%, P: 0.08% or less, S: 0.05% or less, Cr: 20 to 55%, Ni: 20 to 70%, N: 0.001 to 0.25%, O (oxygen): 0.02% or less, and the balance being Fe and impurities.
- (3) The method for manufacturing a metal pipe according to the above item (2), wherein
the metal pipe further contains at least one selected from the elements, by mass percent, given in the following items (a) to (g):- (a) Cu: 5% or less
- (b) Co: 5% or less
- (c) At least one selected from Mo: 3% or less, W: 6% or less, and Ta: 6% or less
- (d) One or two selected from Ti: 1% or less and Nb: 2% or less
- (e) At least one selected from B: 0.1% or less, Zr: 0.1% or less, and Hf: 0.5% or less
- (f) At least one selected from Mg: 0.1 % or less, Ca: 0.1 % or less, and Al: 1% or less
- (g) At least one selected from Y: 0.15% or less and Ln group elements: 0.15% or less.
- (4) The method for manufacturing a metal pipe according to any one of the above items (1) to (3), wherein the metal pipe has a rib-shaped protrusion on the inner surface of pipe.
- According to the present invention, a metal pipe having an oxide scale layer consisting mainly of Cr formed uniformly on the inner surface of the metal pipe can be manufactured. The metal pipe obtained by the manufacturing method of the present invention is excellent in carburization resistance and coking resistance in a carburizing gas environment.
- The present invention provides a method for manufacturing a metal pipe according to claim 1, wherein the inner surface of a metal pipe having a predetermined chemical composition is subjected to mechanical treatment; the metal pipe is subjected to heat treatment such as to be held in a temperature range of 1050 to 1270°C for 0.5 to 60 minutes; and thereby an oxide scale layer consisting mainly of Cr is formed on at least the inner surface of the metal pipe. Hereunder, the chemical composition of the metal pipe obtained by the manufacturing method of the present invention, and the mechanical treatment and heat treatment to which the metal pipe is subjected are described. In the description below, "%" relating to the content of each element means "mass %".
- The metal pipe obtained by the manufacturing method of the present invention must contain 20 to 55% of Cr and 20 to 70% of Ni.
- Cr (Chromium) must be contained in an amount of at least 20%. The reason is that the oxide scale layer consisting mainly of Cr is formed stably on at least the inner surface of the metal pipe. However, if Cr is contained excessively, it is difficult to manufacture the metal pipe, and the micro-structure may become unstable during the use at high temperature. Therefore, the upper limit of Cr content is set to 55%. To ensure the workability and to prevent the structural stability from deteriorating, the upper limit of Cr content is preferably set to 35%. The further preferable range of Cr content is 22 to 33%.
- Ni (Nickel) is an element necessary for obtaining a stable austenitic structure. Ni should be contained in an appropriate amount depending on the Cr content. Ni has an effect of reducing the intrusion rate of carbon into the metal material. This effect is achieved in the case where the Ni content is set to at least 20%. However, even if Ni is added excessively, the effect saturates, and the manufacturing cost is increased. Excessive Ni makes the manufacture of pipe difficult. Therefore, the Ni content is set to 20 to 70%. The lower limit of Ni content is preferably set to 23%, and the upper limit thereof is preferably set to 60%, further preferably 50%.
- The starting material for a metal pipe for manufacturing ethylene (ethylene cracking tube) preferably contains Cr: 20 to 35% and Ni: 20 to 60%.
- The metal pipe obtained by the manufacturing method of the present invention has the above-described chemical composition, and other components are not limited. However, the metal pipe preferably has a chemical composition consisting of C: 0.01 to 0.6%, Si: 0.1 to 5%, Mn: 0.1 to 10%, P: 0.08% or less, S: 0.05% or less, Cr: 20 to 55%, Ni: 20 to 70%, N: 0.001 to 0.25%, O (oxygen): 0.02% or less, the balance being Fe and impurities. Hereunder, the reasons for restricting the content of each element are described.
- The impurities are components that mixedly enter from raw ore, scrap, and the like when the metal pipe is manufactured on an industrial basis, and are permitted as far as the content range does not adversely affect the present invention.
- C (Carbon) is an element effective in ensuring the high-temperature strength. This effect is remarkable when at least 0.01% of C is contained. If the C content exceeds 0.6%, the toughness may be deteriorated extremely. Therefore, the C content is preferably set to 0.01 to 0.6%. The lower limit of C content is further preferably set to 0.02%, and the upper limit thereof is further preferably set to 0.45%, still further preferably 0.3%.
- Si (Silicon) has an effect of assisting the uniform formation of the oxide scale layer consisting mainly of Cr because the affinity of Si for oxygen is high. This effect is remarkable when at least 0.1% of Si is contained. However, if the Si content exceeds 5%, the weldability is deteriorated, and the micro-structure may become unstable. Therefore, the Si content is preferably set to 0.1 to 5%. The upper limit of Si content is preferably set to 3%, further preferably 2%, and the lower limit thereof is preferably set to 0.3%.
- Mn (Manganese) is an element effective for deoxidation and in improving the workability. Also, because Mn is an austenite producing element, some of Ni can be replaced with Mn. To achieve these effects, at least 0.1 % of Mn is preferably contained. However, if Mn is contained excessively, the formation of the oxide scale layer consisting mainly of Cr may be hindered. Therefore, the Mn content is preferably set to 0.1 to 10%. The upper limit of Mn content is preferably set to 5%, further preferably 2%.
- P (Phosphorus) and S (Sulfur) are preferably reduced in amount as far as possible because these elements segregate at the crystal grain boundary and deteriorate the hot workability. However, because the excessive reduction leads to an increase in cost, the P content is preferably 0.08% or less, and the S content is preferably 0.05% or less. The P content is further preferably set to 0.05% or less, and the S content is further preferably set to 0.03% or less. The P content is still further preferably set to 0.04% or less, and the S content is still further preferably set to 0.015% or less.
- N (Nitrogen) is an element effective in improving the high-temperature strength. This effect is remarkable when at least 0.001% of N is contained. However, the excessive addition of N may hinder the workability greatly. Therefore, the N content is preferably set to 0.001 to 0.25%. The upper limit of N content is preferably set to 0.2%.
- O (Oxygen) is an element existing as an impurity. If the O content exceeds 0.02%, the oxide-base inclusions in the metal material precipitate in large amounts, which decrease the workability, so that the inclusions are a cause for the surface defects of pipe. Therefore, the O content is preferably set to 0.02% or less.
- The above-described metal pipe may further contain one or more elements selected from the elements given in the items (a) to (g) listed below.
- Cu (Copper) is an element for stabilizing the austenitic phase. Cu is also an element effective in improving the high-temperature strength. Therefore, Cu may be contained in the above-described metal pipe. However, if the Cu content is excessive, the hot workability may be decreased. Therefore, if Cu is contained, the content thereof is preferably set to 5% or less. The upper limit of the Cu content is further preferably set to 3%. The above-described effects are remarkable when 0.1% or less of Cu is contained.
- Co (Cobalt) is an element for stabilizing the austenitic phase. If Co is contained, some of Ni can be replaced with Co. Therefore, Co may be contained in the above-described metal pipe. However, if the Co content is excessive, the hot workability may be decreased. Therefore, if Co is contained, the content thereof is preferably set to 5% or less. The upper limit of the Co content is further preferably set to 3%. The above-described effect is remarkable when 0.1 % or less of Co is contained.
- Mo (Molybdenum), W (Tungsten) and Ta (Tantalum) are elements contributing to solid-solution strengthening and effective in improving the high-temperature strength. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the workability is deteriorated, and the structural stability may be hindered. Therefore, if at least one of these elements is contained, the Mo content is preferably set to 3% or less, and the W and Ta contents each are preferably set to 6% or less. The upper limit of each of these elements is further preferably set to 2.5%, still further preferably 2% or less. For each of these elements, the above-described effects are remarkable when at least 0.01% of each of these elements is contained. When these elements are contained compositely, the upper limit of the total amount is preferably set to 10%.
- Ti (Titanium) and Nb (Niobium) have great effects of improving the high-temperature strength, ductility, and toughness even if minute amounts of them are contained. Therefore, one or two selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the workability and weldability may be deteriorated. Therefore, if one or two of these elements are contained, the Ti content is preferably set to 1% or less, and the Nb content is preferably set to 2% or less. For each of these elements, the above-described effects are remarkable when at least 0.01 % of each of these elements is contained. When these elements are contained compositely, the upper limit of the total amount is preferably set to 2%.
- B (Boron), Zr (Zirconium) and Hf (Hafnium) are elements effective in strengthening the grain boundary and improving the hot workability and high-temperature strength. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the weldability may be deteriorated. Therefore, if at least one of these elements is contained, the B and Zr contents each are preferably set to 0.1% or less, and the Hf content is preferably set to 0.5% or less. For each of these elements, the above-described effects are remarkable when at least 0.001% of each of these elements is contained. When these elements are contained compositely, the upper limit of the total amount is preferably set to 0.3%.
- Mg (Magnesium), Ca (Calcium) and Al (Aluminum) are elements effective in improving the hot workability. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the weldability may be deteriorated. Therefore, if at least one of these elements is contained, the Mg content is preferably set to 0.1% or less, the Ca content is preferably set to 0.1% or less, and the Al content is preferably set to 1% or less. The upper limits of the Mg content and the Ca content each are further preferably set to 0.05%, and the upper limit of the Al content is further preferably set to 0.6%. The above-described effect is remarkable when at least 0.001% of each of Mg and Ca is contained and when at least 0.01% of A1 is contained. The lower limits of the Mg content and the Ca content each are preferably set to 0.002%. When these elements are contained compositely, the upper limit of the total amount is preferably set to 0.5%.
- Y (Yttrium) and Ln (Lanthanide) group elements are elements effective in improving the oxidation resistance. Therefore, at least one selected from these elements may be contained in the above-described metal pipe. However, if the contents of these elements are excessive, the workability is deteriorated. Therefore, if at least one of these elements is contained, the content of each element is preferably set to 0.15% or less. The above-described effect is remarkable when at least 0.0005% of each of these elements is contained. The upper limit of the content of each of these elements is further preferably set to 0.10%. When these elements are contained compositely, the upper limit of the total amount is preferably set to 0.15%. The Ln group elements are elements of La, which is element number 57, through Lu, which is element number 71. Among the Ln group elements, at least one of La, Ce and Nd is preferably used.
- When the metal pipe is worked, a lubricant is used to reduce the friction between the metal pipe and a working tool. The lubricant is usually removed by degreasing and cleaning after working. However, some of the lubricant remains on the inner surface of pipe. As described above, the lubricant remaining on the surface of the metal pipe hinders the formation of the oxide scale layer consisting mainly of Cr. In the present invention, therefore, mechanical treatment is performed to remove the remaining lubricant. In some cases, in addition to the lubricant, the oxide scale produced at the time of hot pipe-making, dirt, and the like are adhered and remain on the surface of the metal pipe. Such remainder is preferably removed because it hinders the uniform formation of the oxide scale layer consisting mainly of Cr.
- The mechanical treatment is treatment for enhancing the cleanliness of the inner surface of the metal pipe by physically removing deposits such as the lubricant remaining on the surface of the metal pipe, dirt, and oxide scale. The mechanical treatment includes, for example, blasting treatment, grinding treatment (or friction treatment) for removing the deposits by bringing an abrasive into direct contact with the inner surface of metal pipe and rubbing the inner surface thereof with the abrasive, and a process for removing the deposits by spraying high-pressure water without the use of abrasive. As the blasting treatment, for example, there are available air-blasting in which blast media are propelled by compressed air, sandblasting (one kind of air-blasting) in which sand is used as the blast media, shotblasting in which blast media are propelled by the centrifugal force of an impeller made of an abrasion-resistant alloy, shotpeening (one kind of shotblasting) mainly used for giving strain to the metal surface, wet blasting, and the like. In the shotpeening, deposits on the surface can be removed simultaneously with the giving of strain. Wet blasting in which blast media are propelled together with high-pressure water can also be applied.
- Although the abrasive used for the mechanical treatment is not limited, a nonmetal such as silica sand (SiO2), alumina (Al2O3), zirconia (ZrO2), boron nitride (BN), or silicon carbide (SiC), a mixture of these nonmetals or an abrasive containing these nonmetals as principal components is suitably used. Also, an abrasive consisting of a metal such as cast steel, stainless steel, metallic glass (amorphous), or Cr may be used. A nonwoven fabric or the like to which the abrasive is stuck may also be used. The shape of the abrasive is not limited, and the abrasive can take any shape such as a granular shape, a grit shape, or a powder shape. The size of the abrasive is not limited. However, in the case where the surface roughness is restrained to enhance the coking resistance, the average grain size (the average of the major axis and the minor axis) is preferably 300 µm or less, further preferably 150 µm or less.
- In the case where the above-described abrasive is shot blasted onto the inner surface of pipe at a high speed, the abrasive may be shot blasted from one end or both ends of the metal pipe, or may be shot blasted while a blasting nozzle is inserted into the metal pipe and is moved in the pipe. Alternatively, the abrasive or the nonwoven fabric to which the abrasive is stuck may be brought into direct contact with the inner surface of metal pipe in a state of being dry or being wetted by a liquid and may be moved while rubbing the inner surface of metal pipe.
- The metal pipe is subjected to mechanical treatment, subsequently heat treatment, and thereby an oxide scale layer consisting mainly of Cr is formed on the inner surface of the metal pipe. If the heat treatment temperature is lower than 1050°C, the oxide scale layer formed on the surface of metal pipe is thin, so that the shielding property against the intrusion of carbon into metal material is insufficient. If the heat treatment temperature exceeds 1270°C, pores or cracks are occurred in the oxide scale layer, and the denseness is decreased, which results in a decrease in carburization resistance. Therefore, the heat treatment is performed in the temperature range of 1050 to 1270°C. The lower limit of heat treatment temperature is preferably 1120°C, further preferably 1160°C.
- If the holding time of the heat treatment is shorter than 0.5 minute, the oxide scale layer consisting mainly of Cr excellent in carburization resistance cannot be formed uniformly. Even if the holding time exceeds 60 minutes, the thickness of the oxide scale layer merely increases, which leads to a decrease in productivity and an increase in energy cost. Moreover, there also arises a problem of decreased denseness of the oxide scale layer. Therefore, the holding time in the above-described temperature range is set to 0.5 to 60 minutes. The lower limit of the holding time is preferably set to 2 minutes, further preferably 5 minutes. The upper limit of the holding time is preferably set to 30 minutes, further preferably 15 minutes.
- It is preferable to encourage degreasing, cleaning, pickling, and other treatment after the mechanical treatment. Even if heat treatment is performed after these kinds of treatment, the uniform formation of the oxide scale layer consisting mainly of Cr is not hindered. These kinds of treatment are especially effective in the case where there is a concern about decrease in cleanliness caused by the abrasive remaining on the inner surface of pipe. The gas atmosphere in the heat treatment may be any atmosphere in which the oxide scale layer consisting mainly of Cr can be formed. For example, the atmosphere of atmospheric gas or a gas obtained by burning a hydrocarbon fuel (LNG, butane, etc.) and air may be used. Also, the atmosphere of DX gas, NX gas, RX gas, COG (C gas), or hydrogen gas whose dew point is controlled may be used. The atmosphere of a gas obtained by mixing these gases in an arbitrary ratio may also be used.
- The oxide scale layer consisting mainly of Cr is very important from the viewpoints of carburization resistance and coking resistance. In particular, the oxide scale layer containing at least 50% of Cr has a high denseness and is excellent in shielding property against the intrusion of carbon into metal material. The oxide scale layer consisting mainly of Cr restrains coking on the surface of metal material because the catalytic action thereof against coking is weak. As a result, the thermal conductivity to a fluid in the pipe is kept for a long period of time. For example, in the case where the metal pipe is used as a decomposition reaction tube, the yield of a reaction product such as olefin is stabilized.
- The Cr content in the oxide scale layer is preferably at least 80%. The oxide scale layer having a high Cr content is denser and achieves a great effect of shielding the intrusion of carbon into the metal material. The content of element in the oxide scale layer can be measured by EDX. The measurement should be made from the surface of the oxide scale layer. The determination of element is made by the fraction of the detected element excluding C (carbon), O (oxygen), and the like.
- The present invention is especially useful in manufacture of a metal pipe having a rib-shaped protrusion on the inner surface thereof. Usually, in the case of such a metal pipe having a rib-shaped protrusion on the inner surface thereof, it is thought that the metal pipe is liable to be attacked by carburizing gas, and the oxide scale is liable to peel off. According to the present invention, however, a metal pipe having high carburization resistance on the inner surface of the pipe and high repairability of the film can be obtained. A pipe having a protrusion on the inner surface thereof, a pipe having fins, and the like are cited as the pipe having the rib-shaped protrusion. The protrusion, the fin, and the like may be formed integrally with the pipe itself or may be formed by welding or the like means.
- The present invention is explained below more specifically by way of example. The present invention is not limited to the example.
- Metal materials having the chemical composition given in Table 1 were melted by using an electric furnace or a vacuum furnace to form billets. The obtained billets were hot forged and cold rolled to produce metal pipes having an outside diameter of 56 mm and a wall thickness of 6 mm. The metal pipes of specimen Nos. 1 to 10 were subjected to mechanical treatment of the conditions given in Table 2. For some metal pipes, the mechanical treatment was omitted. Then, the metal pipes were subjected to heat treatment under the conditions given in Table 2 to form oxide scale. Some metal pipes were subjected to alumina blasting as the mechanical treatment, and were not subjected to heat treatment. To evaluate uniform carburization resistance and coking resistance in the metal pipe, each of the metal pipes was cut at a total of five places at a 2-m pitch along the pipe longitudinal direction to sample ring-shaped specimens each having a width of 50 mm and specimens for observation of oxide scale (20 x 20 mm square), described later.
TABLE 1 Specimen No. Base metal chemical composition (mass %) C Si Mn P S Cr Ni N O Others 1 0,21 0,36 0,42 0,020 <0.001 25,8 24,5 0,04 0,01 0.5Ti 2 0,11 1,67 0,28 0,017 <0.001 25,3 38,3 0,02 0,01 1.2Mo, 0.5Ti 3 0,08 0,35 1,20 0,025 <0.001 20,7 30,5 0,02 0,01 - 4 0,11 1,85 3,20 0,022 0,001 28,9 42,5 0,05 <0.01 1.3Nb, 0.003Ca 5 0,01 0,12 0,15 0,018 <0.001 31,2 60,8 0,01 0,01 0.004B, 0.029La 6 0,12 1,54 0,32 0,022 <0.001 25,6 38,3 0,02 0,01 1.0W, 1.1Cu, 0.01Y 7 0,11 1,48 0,36 0,020 <0.001 24,8 38,5 0,02 0,01 0.004Mg, 0.55Co 8 0,12 1,61 0,34 0,017 <0.001 25,7 38,5 0,02 <0.01 0.04Al, 0.02Zr 9 0,11 1,55 0,64 0,025 <0.001 25,2 38,1 0,01 <0.01 1.3Ta, 0.2Hf 10 0,11 0,46 1,31 0,025 0,001 *18.6 25,5 0,03 0,01 - * indicates a value deviating from the range defined in the present invention. - EDX analysis was made from the surface of the specimen for observation, and the Cr content (mass %) in the oxide scale layer produced on the metal pipe was determined from the average of three measurements. On the other hand, carburization and coking tests were conducted by holding the ring-shaped specimen at 1000°C for 300 hours in the gas atmosphere of 15%CH4-3%CO2-82%H2 by a volume ratio. Concerning the coking resistance, the mass of specimen was measured before and after the test to determine the increase amount due to coke deposit, and deposited coke amount per unit area (mg/cm2) was determined. Concerning the carburization resistance, the amount of C intruding into the base metal was evaluated. That is, metal chips were sampled at a 0.5-mm pitch in the depth direction from the surface of the specimen having been tested, and the amount of C (mass %) at a depth of 0.5 to 1.0 mm and the amount of C (mass %) at a depth of 1.0 to 1.5 mm were measured by chemical analysis. After the amount of C (mass %) of base metal before testing was subtracted, the average value of both the amounts of C was defined as the amount of intruding C (mass %) at a depth of 1 mm.
- The metal pipe that meets the following criteria for all items was accepted:
- (1) Oxide scale layer consisting mainly of Cr:
- Cr concentration in EDX analysis ≥ 50 mass %
- (2) Carburization resistance:
- Amount of intruding C at 1-mm depth ≤ 1.5 mass %
- (3) Coking resistance:
- Amount of deposited C ≤ 3 mg/cm2.
- These results are summarized in Table 2.
TABLE 2 No. Specime n No. Blasting treatment Heat treatment Oxide scale layer consisting mainly of Cr Carburization resistance Coking resistance Classification Abrasive Treatment method Temperature /time Gas atmosphere 1 1 Silica sand Blasting 1180°C/15min LNG burning 5/5 5/5 5/5 Present invention example 2 Cast steel Blasting 1270°C/ 3 min LNG burning 5/5 5/5 5/5 Present invention example 3 2 Silica sand Blasting 1200°C/ 8min Air 5/5 5/5 5/5 Present invention example 4 Alumina Blasting 1230°C/ 6min Air 5/5 5/5 5/5 Present invention example 5 Zirconia Blasting 1200°C/10min Air 5/5 5/5 5/5 Present invention example 6 Cast steel (grit) Blasting 1200°C/15min Air 5/5 5/5 5/5 Present invention example 7 Not performed 1230°C/ 6min Air *3/5 *3/5 *3/5 Comparative example 8 Alumina Blasting 1000°C/15min Air *2/5 *3/5 *3/5 Comparative example 9 Alumina Blasting None *None *3/5 *1/5 Comparative example 10 3 Alumina-zirconia mixture Blasting 1200°C/ 5min Butane burning 5/5 5/5 5/5 Present invention example 11 SiC Grinding 1120°C/30min Butane burning 5/5 5/5 5/5 Present invention example 12 Metal amorphous Blasting 1060°C/60min Butane burning 5/5 5/5 5/5 Present invention example 13 Cast steel Peening 1170°C/10min Butane burning 5/5 5/5 5/5 Present invention example 14 Not performed 1160°C/10min Butane burning *2/5 *2/5 *2/5 Comparative example 15 4 BN Blasting 1220°C/ 8min LNG burning 5/5 5/5 5/5 Present invention example 16 5 Alumina Blasting 1170°C/12min LNG burning 5/5 5/5 5/5 Present invention example 17 6 SiC Wet grinding 1210°C/10min LNG burning 5/5 5/5 5/5 Present invention example 18 7 SiC-alumina stuck nonwoven fabric Friction 1220°C/ 8min LNG burning 5/5 5/5 5/5 Present invention example 19 8 SUS Blasting 1230°C/ 10min LNG burning 5/5 5/5 5/5 Present invention example 20 9 Cr Blasting 1230°C/ 12min Air 5/5 5/5 5/5 Present invention example 21 10 Silica sand Blasting 1200°C/20min LNG burning *0/5 *0/5 *0/5 Comparative example 22 Alumina Blasting 1200°C/10min LNG burning *0/5 *0/5 *0/5 Comparative example * indicates that performance at which present invention aims is not obtained. - The numeral in Table 2 denotes the number of specimens meeting the criteria of the above items (1), (2) and (3) per five specimens. For example, 3/5 denotes that three of five are acceptable. The present invention aims at excellent carburization resistance and coking resistance throughout the overall length of the inner surface of metal pipe. Therefore, it was determined that each of the criteria of the present invention is met when all of the five specimens are acceptable.
- As shown in Table 2, in examples of Nos. 21 and 22 in which specimen No. 10 that did not meet the conditions of chemical composition defined in the present invention was used, although mechanical treatment was performed, the oxide scale layer consisting mainly of Cr could not be obtained, and both oaf the carburization resistance and coking resistance were poor. Of examples using specimen Nos. 2 and 3, in examples of Nos. 7 and 14 in which mechanical treatment was omitted, some of five specimens did not meet the criteria, and the carburization resistance and coking resistance in the pipe longitudinal direction were nonuniform. Of examples using specimen No. 2, in examples of No. 8 in which the heat treatment temperature was low and No. 9 in which heat treatment was not performed, carburization and coking occurred in some of the specimens.
- On the other hand, for all of the specimens that used the metal pipes of specimen Nos. 1 to 9 meeting the conditions of chemical composition defined in the present invention, were subjected to mechanical treatment, and were subjected to heat treatment under the conditions defined in the present invention, all of the criteria of the above items (1), (2) and (3) were met, and the carburization resistance and coking resistance were excellent throughout the overall length in the metal pipe longitudinal direction.
- According to the present invention, a metal pipe having an oxide scale layer consisting mainly of Cr formed uniformly on the inner surface of the metal pipe can be manufactured, so that the metal pipe is excellent in carburization resistance and coking resistance in a carburizing gas environment. For this reason, the metal pipe obtained by the present invention is suitably used especially as a pipe used in a carburizing gas atmosphere containing hydrocarbon gas, CO gas, and the like, such as a pyrolytic furnace pipe, a reforming furnace pipe, a heating furnace pipe, and a heat exchanger pipe in an oil refining plant, a petrochemical plant, and the like.
Claims (2)
- A method for manufacturing a metal pipe containing, by mass percent, 20 to 55% of Cr and 20 to 70% of Ni, and
optionally having a chemical composition consisting of, by mass percent, C: 0.01 to 0.6%, Si: 0.1 to 5%, Mn: 0.1 to 10%, P: 0.08% or less, S: 0.05% or less, Cr: 20 to 55%, Ni: 20 to 70%, N: 0.001 to 0.25%, O (oxygen): 0.02% or less, the balance being Fe and impurities, and
further optionally at least one selected from the elements, by mass percent, given in the following items (a) to (g):(a) Cu: 5% or less(b) Co: 5% or less(c) at least one selected from Mo: 3% or less, W: 6% or less, and Ta: 6% or less(d) one or two selected from Ti: 1% or less and Nb: 2% or less(e) at least one selected from B: 0.1% or less, Zr: 0.1% or less, and Hf: 0.5% or less(f) at least one selected from Mg: 0.1% or less, Ca: 0.1% or less, and Al: 1% or less(g) at least one selected from Y: 0.15% or less and Ln group elements: 0.15% or less,wherein
the inner surface of the metal pipe is subjected to mechanical treatment, thereby physically removing deposits from the inner surface of the metal pipe;
the metal pipe is subsequently subjected to heat treatment in a temperature range of 1050 to 1270°C for 0.5 to 60 minutes; and thereby
an oxide scale layer consisting mainly of Cr is formed on at least the inner surface of the metal pipe. - The method for manufacturing a metal pipe according to claim 1, wherein the metal pipe has a rib-shaped protrusion on the inner surface of pipe.
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RU2527543C1 (en) * | 2013-03-06 | 2014-09-10 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Nickel-based alloy for application of wear and corrosion resistance by micro plasma or cold supersonic spraying |
CN103422003B (en) * | 2013-05-15 | 2015-06-17 | 锡山区羊尖泓之盛五金厂 | Nichrome |
CN103320706B (en) * | 2013-06-05 | 2015-12-02 | 西安交通大学 | A kind of two rare earth modified high temperature steel and preparation method thereof |
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EP2009133A1 (en) * | 2006-04-12 | 2008-12-31 | Sumitomo Metal Industries Limited | METHOD FOR PRODUCING Cr-CONTAINING NICKEL-BASED ALLOY PIPE AND Cr-CONTAINING NICKEL-BASED ALLOY PIPE |
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JPH01259156A (en) * | 1988-04-08 | 1989-10-16 | Sumitomo Metal Ind Ltd | Austenitic stainless steel tube and its production |
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JPH0339461A (en) * | 1989-07-06 | 1991-02-20 | Sumitomo Metal Ind Ltd | Surface treated steel tube excellent in corrosion resistance and heat transfer efficiency and its production |
US5041309A (en) * | 1990-02-28 | 1991-08-20 | The Babcock & Wilcox Company | Method of chromizing a workpiece by applying a coating containing chromium particles onto a ceramic carrier, positioning the carrier proximate the workpiece, and heating both carrier and workpiece to diffuse chromium particles into the workpiece |
JPH0499860A (en) * | 1990-08-15 | 1992-03-31 | Honda Motor Co Ltd | Surface treatment of titanium parts |
WO2000070112A1 (en) * | 1999-05-18 | 2000-11-23 | Sumitomo Metal Industries, Ltd. | Martensite stainless steel for seamless steel tube |
JP4042362B2 (en) * | 2000-08-11 | 2008-02-06 | 住友金属工業株式会社 | Ni-base alloy product and manufacturing method thereof |
JP2003176824A (en) * | 2001-12-11 | 2003-06-27 | Minebea Co Ltd | Fluid dynamic pressure bearing and spindle motor |
JP3960069B2 (en) * | 2002-02-13 | 2007-08-15 | 住友金属工業株式会社 | Heat treatment method for Ni-base alloy tube |
CN1280445C (en) * | 2003-07-17 | 2006-10-18 | 住友金属工业株式会社 | Stainless steel and stainless steel pipe having resistance to carburization and coking |
CA2556128A1 (en) * | 2004-02-12 | 2005-08-25 | Sumitomo Metal Industries, Ltd. | Metal tube for use in a carburizing gas atmosphere |
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2010
- 2010-02-15 CA CA2750014A patent/CA2750014C/en not_active Expired - Fee Related
- 2010-02-15 JP JP2010506734A patent/JP4586938B2/en active Active
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- 2010-02-15 CN CN2010800069933A patent/CN102308015A/en active Pending
- 2010-02-15 WO PCT/JP2010/052165 patent/WO2010093034A1/en active Application Filing
- 2010-02-15 EP EP10741311.4A patent/EP2397573B1/en not_active Not-in-force
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EP2009133A1 (en) * | 2006-04-12 | 2008-12-31 | Sumitomo Metal Industries Limited | METHOD FOR PRODUCING Cr-CONTAINING NICKEL-BASED ALLOY PIPE AND Cr-CONTAINING NICKEL-BASED ALLOY PIPE |
Also Published As
Publication number | Publication date |
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KR20110107370A (en) | 2011-09-30 |
CN102308015A (en) | 2012-01-04 |
JPWO2010093034A1 (en) | 2012-08-16 |
WO2010093034A1 (en) | 2010-08-19 |
US20110308669A1 (en) | 2011-12-22 |
EP2397573A4 (en) | 2012-12-26 |
JP4586938B2 (en) | 2010-11-24 |
CA2750014A1 (en) | 2010-08-19 |
EP2397573A1 (en) | 2011-12-21 |
CA2750014C (en) | 2014-12-02 |
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