NO135595B - - Google Patents
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- NO135595B NO135595B NO63373A NO63373A NO135595B NO 135595 B NO135595 B NO 135595B NO 63373 A NO63373 A NO 63373A NO 63373 A NO63373 A NO 63373A NO 135595 B NO135595 B NO 135595B
- Authority
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- Prior art keywords
- vanadium
- weight
- carbon
- oxygen
- oxycarbide
- Prior art date
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- 229910052720 vanadium Inorganic materials 0.000 claims description 79
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 76
- 229910052799 carbon Inorganic materials 0.000 description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 43
- 239000001301 oxygen Substances 0.000 description 43
- 229910052760 oxygen Inorganic materials 0.000 description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 14
- 239000010959 steel Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 9
- 229910000756 V alloy Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- SUAUKFMZICJTAY-UHFFFAOYSA-N [V].[Fe].[Mn] Chemical compound [V].[Fe].[Mn] SUAUKFMZICJTAY-UHFFFAOYSA-N 0.000 description 1
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- -1 oxy- Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0213—Obtaining thorium, uranium, or other actinides obtaining uranium by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Description
Ved legering av stål med vanadium blir dette metall vanligvis tilsatt til smeltet stål i form av ferro-vanadium. When steel is alloyed with vanadium, this metal is usually added to molten steel in the form of ferro-vanadium.
I de senere år har det vært stor interesse for vanadium-kar-bid som vanadiumholdig materiale for tilsetning til det smel-tede metall. Vanadiumkarbidet kan fremstilles på enkel måte, men tilsetningen av dette materiale vil jo medføre en samtidig tilsetning av karbon, hvilket kan være en ulempe. In recent years, there has been great interest in vanadium carbide as a vanadium-containing material for addition to the molten metal. The vanadium carbide can be produced in a simple way, but the addition of this material will entail a simultaneous addition of carbon, which can be a disadvantage.
Det ville være ønskelig at det vanadiumholdige materiale som anvendes ved fremstillingen av de vanadiumholdige legeringer, er et materiale som kan fremstilles like enkelt som vanadiumkarbid og dessuten har den fordel at lite eller intet karbon samtidig tilsettes legeringen som skal fremstilles. It would be desirable for the vanadium-containing material used in the production of the vanadium-containing alloys to be a material that can be produced as easily as vanadium carbide and also has the advantage that little or no carbon is simultaneously added to the alloy to be produced.
Det er "blitt funnet at slike utgangsmaterialer, som også er egnet til fremstilling av metallisk vanadium av høy-re nhet. It has been found that such starting materials, which are also suitable for the production of high-purity metallic vanadium.
I "Zeitschrift fur Metallkunde",bind 60, februar 1969, s. 94-100, er det beskrevet noen forholdsvis vanske- In "Zeitschrift fur Metallkunde", volume 60, February 1969, pp. 94-100, some relatively difficult
lige og arbeidskrevende fremgangsmåter til fremstilling av visse metaller, herunder vanadium. Det angis at vanadium, simple and labor-intensive methods for the production of certain metals, including vanadium. It is stated that vanadium,
niob og tantal er vanskelige å fremstille, fordi det dannes eutektiske smelter, og det angis enn videre at de i artikkelen beskrevne fremgangsmåter ikke er egnet til fremstilling av titan, zirkonium og hafnium. niobium and tantalum are difficult to produce, because eutectic melts are formed, and it is further stated that the methods described in the article are not suitable for the production of titanium, zirconium and hafnium.
Det ble nå funnet at de ovenfor nevnte metaller It was now found that the above mentioned metals
kan fremstilles ut fra et metalloksykarbid erholdt ved omsetning av et oksyd av disse metaller med et gassformig hydrokarbon. can be produced from a metal oxycarbide obtained by reacting an oxide of these metals with a gaseous hydrocarbon.
Oppfinnelsen angår således en fremgangsmåte ved fremstilling av vanadium, niob, tantal, titan, zirkonium eller hafnium eller en legering av disse metaller med jern, mangan, nikkel eller aluminium, hvor en oksygen- og karbonholdig forbindelse av vanadium, niob, tantal, titan, zirkonium eller hafnium oppvarmes til en temperatur på minst 800°C, eller - ved fremstilling av en legering - hvor den nevnte oksygen- og karbonholdige forbindelse blandés med jern, mangan, nikkel eller aluminium og oppvarmes til en temperatur på minst 800°C, og fremgangsmåten er karakterisert ved at det anvendes en oksygen- og karbonholdig forbindelse som er fremstilt ved omsetning av et oksyd av vanadium, niob, tantal, titan, zirkonium eller hafnium med et gassformig hydrokarbon. The invention thus concerns a method for the production of vanadium, niobium, tantalum, titanium, zirconium or hafnium or an alloy of these metals with iron, manganese, nickel or aluminium, where an oxygen- and carbon-containing compound of vanadium, niobium, tantalum, titanium, zirconium or hafnium is heated to a temperature of at least 800°C, or - in the production of an alloy - where the aforementioned oxygen- and carbon-containing compound is mixed with iron, manganese, nickel or aluminum and heated to a temperature of at least 800°C, and the method is characterized by the use of an oxygen- and carbon-containing compound which is produced by reacting an oxide of vanadium, niobium, tantalum, titanium, zirconium or hafnium with a gaseous hydrocarbon.
Metaller av gruppe V B innbefatter vanadium, niob og tantal, og gruppe IV B innbefatter titan, zirkonium og hafnium. Legeringene kan fremstilles ved at et metalloksykarbid bringes i kontakt med en smelte av ett eller flere andre metaller og/eller metallegeringer og/eller metallforbindelser. En smelte av en metallegering kan eksempelvis være smeltet stål. Legeringer kan også fremstilles ved oppheting av en sammenpresset blanding av et metalloksykarbid med ett eller flere andre metaller og/eller metall-legeringer og/eller metallforbindelser i pulverform. Fremstillingen av legeringer kan utføres under normalt trykk. Metallet fremstilles ved oppheting av oksykarbidet av det angjeldende metall, f.eks. i vI akuoum eller i en inert atmosfære, ved en temperatur over 800 C. Avhengig av hvxlket metall som skal fremstilles, kan temperaturen være høyere, f.eks. minst 1200°C eller minst 1400°C. Ved fremstilling av eksempelvis niob og titan er det imidlertid også mulig å anvende plasma-oppheting, hvorved temperaturer på flere tusen°C kan oppnås, endog opptil 10 000°C. Metals of group V B include vanadium, niobium and tantalum, and group IV B include titanium, zirconium and hafnium. The alloys can be produced by bringing a metal oxycarbide into contact with a melt of one or more other metals and/or metal alloys and/or metal compounds. A melt of a metal alloy can, for example, be molten steel. Alloys can also be produced by heating a compressed mixture of a metal oxycarbide with one or more other metals and/or metal alloys and/or metal compounds in powder form. The production of alloys can be carried out under normal pressure. The metal is produced by heating the oxycarbide of the metal in question, e.g. in vacuum or in an inert atmosphere, at a temperature above 800 C. Depending on the type of metal to be produced, the temperature can be higher, e.g. at least 1200°C or at least 1400°C. However, when producing niobium and titanium, for example, it is also possible to use plasma heating, whereby temperatures of several thousand °C can be achieved, even up to 10,000 °C.
Det er også mulig å anvende to oksykarbider av forskjellige metaller istedenfor ett oksykarbid, hvorved metallegeringer erholdes. I andre tilfeller danner det ene metalloksykarbid en fast oppløsning med det andre metall-oksykarbidet. It is also possible to use two oxycarbides of different metals instead of one oxycarbide, whereby metal alloys are obtained. In other cases, one metal oxycarbide forms a solid solution with the other metal oxycarbide.
Ved fremstillingen av metallet ut fra metalloksy-karbidet er det også mulig å tilsette et metall med en relativt høy flyktighet og et lavt smeltepunkt til oksykarbidet. Ved oppheting i vakuum vil det tilsatte metall forflyktiges. Dette kan også skje med metalloksydet. When producing the metal from the metaloxy carbide, it is also possible to add a metal with a relatively high volatility and a low melting point to the oxycarbide. When heated in a vacuum, the added metal will volatilize. This can also happen with the metal oxide.
Et eksempel på fremstilling av et metalloksykarbid er fremstillingen av vanadiumoksykarbid ut fra et materiale inneholdende oksydisk vanadium ved omsetning med gassformig hydrokarbon (særlig metan), eventuelt i nærvær av andre gasser. Med uttrykket "vanadiumoksykarbid" menes et produkt som hovedsakelig består av forbindelser med formelen VO C , hvor An example of the production of a metal oxycarbide is the production of vanadium oxycarbide from a material containing oxidised vanadium by reaction with a gaseous hydrocarbon (especially methane), possibly in the presence of other gases. The term "vanadium oxycarbide" means a product which mainly consists of compounds with the formula VO C , where
x y x y
summen av x og y tilnærmet er 1. Dessuten kan oksykarbidet inneholde fritt karbon, avhengig av valget av fremstillings-betingeIsene. Oksykarbidet kan også inneholde en liten an-del nitrogen (opptil 4%). Ved anvendelse av gass fra Sloch-teren ved fremstillingen (som inneholder ca. 85% CH^ og 15% N2) vil oksykarbidet ofte inneholde ca. 0,1% nitrogen. the sum of x and y is approximately 1. Furthermore, the oxycarbide may contain free carbon, depending on the choice of manufacturing conditions. The oxycarbide can also contain a small proportion of nitrogen (up to 4%). When using gas from the Sloch teren during production (which contains approx. 85% CH^ and 15% N2), the oxycarbide will often contain approx. 0.1% nitrogen.
Den totale atom-mengde av bundet + fritt karbon i vanadiumoksykarbidet som anvendés ved fremstillingen av vana-diumlegeringene, er fortrinnsvis minst lik atom-mengden av bundet oksygen i oksykarbidet, idet det under opphetingen avgis karbon og oksygen i like atom-mengder (nemlig som karbon-monoksyd), og et støkiometrisk overskudd av oksygen kan medføre at oksygen vil foreligge i legeringen eller at man får tap av vanadium, idet oksydert vanadium går over i slaggen. I noen tilfeller kan man imidlertid bruke et produkt med et støkiometrisk overskudd av oksygen, f.eks. The total atomic amount of bound + free carbon in the vanadium oxycarbide used in the production of the vanadium alloys is preferably at least equal to the atomic amount of bound oxygen in the oxycarbide, since carbon and oxygen are released in equal atomic amounts during heating (namely as carbon monoxide), and a stoichiometric excess of oxygen can mean that oxygen will be present in the alloy or that there will be a loss of vanadium, as oxidized vanadium passes into the slag. In some cases, however, a product with a stoichiometric excess of oxygen can be used, e.g.
når metallet som skal legeres (eksempelvis smeltet stål) allerede inneholder karbon og smeltens karboninnhold kan reduseres. Det atomære forhold mellom vanadiumoksykarbidets innhold av bundet + fritt karbon og dets innhold av oksy- when the metal to be alloyed (for example molten steel) already contains carbon and the carbon content of the melt can be reduced. The atomic ratio between the vanadium oxycarbide's content of bound + free carbon and its content of oxy-
gen bør imidlertid i regeien ikke være mindre enn 0,6. However, gen should not be less than 0.6.
For ikke å innføre alt for meget karbon under fremstillingen av legeringer tilsikter man et atomært forhold mellom bundet + fritt karbon og oksygen i vanadiumoksykarbidet på fortrinnsvis ikke over 2,5 og helst ikke over 1,5. In order not to introduce too much carbon during the production of alloys, one aims for an atomic ratio between bound + free carbon and oxygen in the vanadium oxycarbide of preferably no more than 2.5 and preferably no more than 1.5.
Det atomære forhold mellom bundet karbon og bundet oksygen i vanadiumoksykarbidmåterialet er fortrinnsvis ikke mindre enn 0,9. The atomic ratio between bound carbon and bound oxygen in the vanadium oxycarbide base material is preferably not less than 0.9.
Det er imidlertid mulig å oppnå gode resultater med materialer i hvilke forholdet mellom bundet karbon og bundet oksygen er 0,5 forutsatt at produktet inneholder en tilstrekke-lig mengde fritt karbon, slik at det atomære forhold mellom bundet + fritt karbon og oksygen er minst 0,6 og fortrinnsvis minst 1, idet man har funnet at det frie karbon som kan dannes under fremstillingen av vanadiumoksykarbid ut fra et materiale inneholdende oksydert vanadium og gassformig hydrokarbon, reagerer nesten like så lett med oksygenet i vanadiumoksykarbidet som det bundne karbon. However, it is possible to achieve good results with materials in which the ratio between bound carbon and bound oxygen is 0.5, provided that the product contains a sufficient amount of free carbon, so that the atomic ratio between bound + free carbon and oxygen is at least 0 ,6 and preferably at least 1, as it has been found that the free carbon that can be formed during the production of vanadium oxycarbide from a material containing oxidized vanadium and gaseous hydrocarbon reacts almost as easily with the oxygen in the vanadium oxycarbide as the bound carbon.
De andre metalloksykarbider som anvendes ved fore-liggende fremgangsmåte, fremstilles også ved reduksjon av oksydisk materiale ved hjelp >av gassformig hydrokarbon, eksempelvis nioboksykarbid og titanoksykarbid. The other metaloxycarbides used in the present process are also produced by reduction of oxidic material with the aid of gaseous hydrocarbon, for example nioboxycarbide and titanoxycarbide.
Fremgangsmåten ifølge oppfinnelsen er også anvendelig ved fremstilling av vanadiumholdig stål ved tilsetning av The method according to the invention is also applicable in the production of vanadium-containing steel by adding
.•vanadiumoksykarbid til smeltet stål. .•vanadium oxycarbide for molten steel.
Fremgangsmåten ifølge oppfinnelsen kan imidlertid også med fordel anvendes til fremstilling av vanadiumlegeringer med høyt vanadiuminnhold. Fremgangsmåten kan da utføres både som beskrevet ved tilsetning av vanadiumoksykarbid til en smelte av metallet eller metallene som skal legeres, og i henhold til en annen fremgangsmåte hvor en sammenpresset blanding av pulverformig vanadiumoksykarbid og det metall eller de metaller som skal legeres, opphetes. Begge fremgangsmåter kan utføres under normalt trykk, i noen tilfeller fortrinnsvis i en inert atmosfære (eksempelvis nitrogen). Det er blitt funnet at det i henhold til oppfinnelsen også er mulig å fremstille legeringer av vanadium med metaller (eksempelvis aluminium) som er betydelig mindre edle og følgelig har en høyere affinitet til oksygen enn til vanadium. However, the method according to the invention can also be advantageously used for the production of vanadium alloys with a high vanadium content. The method can then be carried out both as described by adding vanadium oxycarbide to a melt of the metal or metals to be alloyed, and according to another method where a compressed mixture of powdered vanadium oxycarbide and the metal or metals to be alloyed is heated. Both methods can be carried out under normal pressure, in some cases preferably in an inert atmosphere (eg nitrogen). It has been found that according to the invention it is also possible to produce alloys of vanadium with metals (for example aluminum) which are considerably less noble and consequently have a higher affinity to oxygen than to vanadium.
Som nevnt ovenfor kan fremgangsmåten ifølge oppfinnelsen også anvendes til fremstilling av metaller, eksempelvis vanadium, niob eller titan. I denne utførelsesform av fremgangsmåten kan vanadiumoksykarbidet eksempelvis opphetes uten noen ytterligere tilsetning, fortrinnsvis i vakuum. I dette tilfelle vil det atomære forhold mellom karbon (bundet + fritt) og oksygen i vanadiumoksykarbidet bestemme renheten av det vanadium som fåes. I førsøket med vanadium fikk man således et vanadium-metall med et oksygeninnhold på 0,4 % og et karboninnhold på mindre enn 0,1 %. As mentioned above, the method according to the invention can also be used for the production of metals, for example vanadium, niobium or titanium. In this embodiment of the method, the vanadium oxycarbide can, for example, be heated without any further addition, preferably in a vacuum. In this case, the atomic ratio between carbon (bonded + free) and oxygen in the vanadium oxycarbide will determine the purity of the vanadium obtained. In the preliminary trial with vanadium, a vanadium metal was thus obtained with an oxygen content of 0.4% and a carbon content of less than 0.1%.
Som nevnt ovenfor kan fremgangsmåten ifølge oppfinnelsen også anvendes ved fremstilling av metallisk vanadium. I denne utførelsesform kan vanadiumoksykarbidet opphetes uten ytterligere tilsetninger, fortrinnsvis i vakuum. I dette tilfelle vil det atomære forhold mellom karbon (bundet + fritt) As mentioned above, the method according to the invention can also be used in the production of metallic vanadium. In this embodiment, the vanadium oxycarbide can be heated without further additions, preferably in a vacuum. In this case, the atomic ratio of carbon (bonded + free)
og oksygen i vanadiumoksykarbidet bestemme renheten av det vanadium-metall som fåes, og dette forhold er fortrinnsvis ca. 1. and oxygen in the vanadium oxycarbide determine the purity of the vanadium metal that is obtained, and this ratio is preferably approx. 1.
I en annen utførelsesform av fremgangsmåten til fremstilling av metallisk vanadium opphetes vanadiumoksykarbidet i nærvær av et metall som er relativt flyktig og har et lavt smeltepunkt, hvorved det dannes en legering av vanadium og dette metall. Det relativt flyktige metall kan så fjernes fra legeringen ved oppheting i vakuum. Et egnet metall i denne utførelsesform er eksempelvis mangan. In another embodiment of the method for producing metallic vanadium, the vanadium oxycarbide is heated in the presence of a metal which is relatively volatile and has a low melting point, whereby an alloy of vanadium and this metal is formed. The relatively volatile metal can then be removed from the alloy by heating in a vacuum. A suitable metal in this embodiment is, for example, manganese.
De følgende eksempler vil ytterligere belyse oppfinnelsen. The following examples will further illustrate the invention.
Eksempel I Example I
Vanadiumoksykarbid fremstilt ved at man ledet naturgass over teknisk vanadiumpentoksyd inneholdende 67,4 vekt% vanadium, 19,7 vekt% oksygen og 10,3 vekt% karbon ved en temperatur mellom 800 og 1250°C, ble tilsatt til smeltet stål med et oksygeninnhold på 0,04 vekt% og et karboninnhold på Vanadium oxycarbide produced by passing natural gas over technical vanadium pentoxide containing 67.4 wt% vanadium, 19.7 wt% oxygen and 10.3 wt% carbon at a temperature between 800 and 1250°C was added to molten steel with an oxygen content of 0.04% by weight and a carbon content of
0,06 vekt%, i et vektsforhold på 1 : 195 ved en temperatur på ca. 1600°C. Etter kjøling inneholdt stålet 0,34 vekt% vanadium, 0,04 vekt% oksygen og 0,01 vekt% karbon, dvs. et utbytte med hensyn til vanadium tilsvarende 98 %. 0.06% by weight, in a weight ratio of 1:195 at a temperature of approx. 1600°C. After cooling, the steel contained 0.34% by weight vanadium, 0.04% by weight oxygen and 0.01% by weight carbon, i.e. a yield with regard to vanadium corresponding to 98%.
Eksempel II Example II
Vanadiumoksykarbid fremstilt ved at man ledet naturgass over vanadiumpentoksyd inneholdende 70,3 vekt% vanadium. Vanadium oxycarbide produced by passing natural gas over vanadium pentoxide containing 70.3% by weight of vanadium.
22,4 vekt% oksygen og 6,8 vekt% karbon ble, sammen med aluminium, tilsatt til smeltet stål med et oksygeninnhold på 0,04 vekt% 22.4 wt% oxygen and 6.8 wt% carbon were, together with aluminum, added to molten steel with an oxygen content of 0.04 wt%
og et karboninnhold på 0,06 vekt% ved en temperatur på ca. 1600°C i et vektsforhold på 1 : 0,1 : 215. Etter kjøling inneholdt stålet 0,32 vekt% vanadium, 0,03 vekt% oksygen og 0,01 vekt% karbon, dvs. et vanadiumutbytte tilsvarende 98 %. and a carbon content of 0.06% by weight at a temperature of approx. 1600°C in a weight ratio of 1:0.1:215. After cooling, the steel contained 0.32% by weight vanadium, 0.03% by weight oxygen and 0.01% by weight carbon, i.e. a vanadium yield corresponding to 98%.
Eksempel III Example III
72,0 vektdeler vanadiumoksykarbid fremstilt ved at 72.0 parts by weight of vanadium oxycarbide prepared by at
man ledet naturgass over vanadiumpentoksyd inneholdende 74,3 vekt% vanadium, 10,5 vekt% oksygen og 14,5 vekt% karbon ble tilsatt til 99,5 vektdeler smeltet jern ved en temperatur på natural gas was passed over vanadium pentoxide containing 74.3% by weight vanadium, 10.5% by weight oxygen and 14.5% by weight carbon was added to 99.5 parts by weight molten iron at a temperature of
ca. 1600°C. Det erholdte ferrovanadium inneholdt etter kjøling 33,7 vekt% vanadium, 0,02 vekt% oksygen og 2,4 vekt% karbon. about. 1600°C. The ferrovanadium obtained contained, after cooling, 33.7% by weight of vanadium, 0.02% by weight of oxygen and 2.4% by weight of carbon.
Eksempel IV Example IV
33,2 vektdeler vanadiumoksykarbid fremstilt ved at 33.2 parts by weight of vanadium oxycarbide prepared by at
man ledet naturgass over vanadiumpentoksyd inneholdende 73,3 vekt% vanadium, 15 vekt% oksygen og 10,1 vekt% karbon ble blandet med 6,2 vektdeler jernpulver, og blandingen ble presset til en tablett. Denne ble opphetet til en temperatur på ca. 1800°C og holdt ved denne temperjatur i 7 minutter, og det således erholdte ferro-vanadium inneholdt 72,5 vekt% vanadium, natural gas was passed over vanadium pentoxide containing 73.3% by weight vanadium, 15% by weight oxygen and 10.1% by weight carbon was mixed with 6.2 parts by weight iron powder, and the mixture was pressed into a tablet. This was heated to a temperature of approx. 1800°C and held at this temperature for 7 minutes, and the ferro-vanadium thus obtained contained 72.5% by weight of vanadium,
3,3 vekt% oksygen og 2,4 vekt% karbon. 3.3 wt% oxygen and 2.4 wt% carbon.
Eksempel V Example V
17 vektdeler vanadiumoksykarbid fremstilt ved at man ledet naturgass over vanadiumpentoksyd inneholdende 64,2 vekt% vanadium, 13,0 vekt% oksygen og 21,6 vekt% karbon ble blandet med 17 vektdeler jernpulver, hvoretter blandingen ble presset til en tablett, som deretter ble holdt ved 1530°C i 10 minutter. Det erholdte produkt, som inneholdt 37,7 vekt% vanadium, 1,7 vekt% oksygen og 7,2 vekt% karbon, ble tilsatt til smeltet stål i et vektsforhold på 1 : 135. Etter kjøling inneholdt stålet 0,28 vekt% vanadium, mindre enn 0,01 vekt% oksygen og 0,12 17 parts by weight of vanadium oxycarbide prepared by passing natural gas over vanadium pentoxide containing 64.2% by weight vanadium, 13.0% by weight oxygen and 21.6% by weight carbon was mixed with 17 parts by weight of iron powder, after which the mixture was pressed into a tablet, which was then held at 1530°C for 10 minutes. The product obtained, which contained 37.7 wt% vanadium, 1.7 wt% oxygen and 7.2 wt% carbon, was added to molten steel in a weight ratio of 1:135. After cooling, the steel contained 0.28 wt% vanadium , less than 0.01 wt% oxygen and 0.12
vekt% karbon, dvs. at vanadiumutbyttet var 100 %. weight% carbon, i.e. that the vanadium yield was 100%.
Eksempel VI Example VI
Ferrioksyd ble oppløst i smeltet teknisk vanadiumpentoksyd, og etter kjøling erholdtes et produkt inneholdende 44,4 vekt% vanadium, 14,6 vekt% jern og 40,2 vekt% oksygen. Naturgass ble ledet over dette produkt i 4 timer ved en ;emperatur på 600°C og deretter i 6 timer ved 1000°C. Det resulterende jern-vanadium-oksykarbyd inneholdt 53,6 vekt% vanadium, 18,3 vekt% jern, 14,1 vekt% oksygen og 12,0 vekt% karbon (7,9 vekt% var fritt karbon). Ferric oxide was dissolved in molten technical vanadium pentoxide, and after cooling a product containing 44.4% by weight of vanadium, 14.6% by weight of iron and 40.2% by weight of oxygen was obtained. Natural gas was passed over this product for 4 hours at a temperature of 600°C and then for 6 hours at 1000°C. The resulting iron-vanadium oxycarbide contained 53.6 wt% vanadium, 18.3 wt% iron, 14.1 wt% oxygen and 12.0 wt% carbon (7.9 wt% was free carbon).
Det erholdte materiale ble malt og presset til en The material obtained was ground and pressed into a
tablett som deretter ble opphetet og holdt ved ca. 1300°C i 4 minutter. Det resulterende produkt inneholdt 61,9 vekt% vanadium, 9,0 vekt% oksygen og 7,3 vekt% karbon. Dette materiale ble oppløst i smeltet stål i et vektsforhold på 1 : 440 ved ca. 1600°C. Etter kjøling inneholdt stålet 0,14 vekt% vanadium, 0,01 vekt% oksygen og 0,02 vekt% karbon, dvs. at vanadiumutbyttet var 100 %. tablet which was then heated and kept at approx. 1300°C for 4 minutes. The resulting product contained 61.9 wt% vanadium, 9.0 wt% oxygen and 7.3 wt% carbon. This material was dissolved in molten steel in a weight ratio of 1:440 at approx. 1600°C. After cooling, the steel contained 0.14% by weight vanadium, 0.01% by weight oxygen and 0.02% by weight carbon, i.e. the vanadium yield was 100%.
Eksempel VII Example VII
19 vektdeler av det samme vanadium-oksykarbid som ble anvendt i eksempel V, ble blandet med 19 vektdeler ferro-mangan-pulver inneholdende 79,8 vekt% mangan. Blandingen ble presset til en tablett som deretter ble opphetet og holdt ved 1200°C i 9 minutter, hvorved man fikk en jern-mangan-vanadium-legering. 19 parts by weight of the same vanadium oxycarbide used in example V was mixed with 19 parts by weight of ferro-manganese powder containing 79.8% by weight of manganese. The mixture was pressed into a tablet which was then heated and held at 1200°C for 9 minutes, whereby an iron-manganese-vanadium alloy was obtained.
Eksempel VIII Example VIII
10,8 vektdeler vanadiumoksykarbid fremstilt ved at man ledet naturgass over vanadiumpentoksyd inneholdende 73,6 vekt% vanadium, 15,3 vekt% oksygen og 9,6 vekt% karbon ble blandet med 29,6 vektdeler nikkelpuIver, hvoretter blandingen ble presset til en tablett, -som deretter ble holdt ved 1600°C i 6 minutter. Den erholdte nikke1-vanadium-legering inneholdt 78,5 vekt% nikkel, 21,5 vekt% vanadium, 0,03 vekt% oksygen og 0,005 vekt% karbon. 10.8 parts by weight of vanadium oxycarbide prepared by passing natural gas over vanadium pentoxide containing 73.6% by weight vanadium, 15.3% by weight oxygen and 9.6% by weight carbon was mixed with 29.6 parts by weight of nickel powder, after which the mixture was pressed into a tablet , -which was then held at 1600°C for 6 minutes. The nickel-vanadium alloy obtained contained 78.5 wt% nickel, 21.5 wt% vanadium, 0.03 wt% oxygen and 0.005 wt% carbon.
Eksempel IX Example IX
26,0 vektdeler vanadiumoksykarbid fremstilt ved at man ledet naturgass over vanadiumpentoksyd inneholdende 75,7 vekt% vanadium, 9,1 vekt% oksygen og 12,5 vekt% karbon ble tilsatt til 58,8 vektdeler smeltet aluminium, hvoretter denne smelte ble opphetet til en temperatur på 1600°C. Etter kjøling fikk man en aluminium-vanadium-legering inneholdende 21,0 vekt% vanadium, 1,5 vekt% oksygen og 1,7 vekt% karbon. 26.0 parts by weight of vanadium oxycarbide produced by passing natural gas over vanadium pentoxide containing 75.7% by weight vanadium, 9.1% by weight oxygen and 12.5% by weight carbon was added to 58.8 parts by weight of molten aluminium, after which this melt was heated to a temperature of 1600°C. After cooling, an aluminum-vanadium alloy containing 21.0 wt% vanadium, 1.5 wt% oxygen and 1.7 wt% carbon was obtained.
Eksempel X Example X
10,0 vektdeler vanadiumoksykarbid fremstilt ved at man ledet naturgass over vanadiumpentoksyd inneholdende 14,0 vekt% oksygen og 10,5 vekt% karbon ble presset til en tablett og opphetet til en temperatur på 1600°C i en vakuumovn og holdt ved denne temperatur i 5 timer. Det endelige trykk var IO<-5> mm Hg. Det erholdte vanadium-metall inneholdt etter kjøling mindre enn 0,15 vekt% oksygen og mindre enn 0,15 vekt% karbon. 10.0 parts by weight of vanadium oxycarbide produced by passing natural gas over vanadium pentoxide containing 14.0% by weight oxygen and 10.5% by weight carbon was pressed into a tablet and heated to a temperature of 1600°C in a vacuum oven and held at this temperature for 5 hours. The final pressure was 10<-5> mm Hg. The vanadium metal obtained contained after cooling less than 0.15% by weight of oxygen and less than 0.15% by weight of carbon.
Eksempel XI Example XI
3,64 g nioboksykarbid inneholdende 12 vekt% oksygen og 3,5 vekt% karbon ble opphetet til 1600°C i en vakuumovn og holdt ved denne temperatur i 4 timer. Det endelige trykk 3.64 g of nioboxycarbide containing 12% by weight oxygen and 3.5% by weight carbon was heated to 1600°C in a vacuum furnace and held at this temperature for 4 hours. The final print
-4 i -4 in
var 10 mm Hg. Det pulverformige niob inneholdt etter kjøling 4,2 vekt% oksygen og 0,3 vekt% karbon. was 10 mm Hg. After cooling, the powdered niobium contained 4.2% by weight of oxygen and 0.3% by weight of carbon.
Eksempel XII Example XII
3,27 g titanoksykarbid inneholdende 14,8 vekt% oksygen og 11,5 vekt% karbon og dessuten 13 vekt% nikkelpulver ble presset til en tablett og opphetet til 1700°C i vakuumovn og holdt ved denne temperatur i 1,5 timer og deretter ved 1900°C i ytterligere 2 timer. Det endelige trykk var IO<-1> mm Hg. Etter kjøling fikk man titan-metall som inneholdt 7,5 vekt% oksygen og 4,7 vekt% karbon og mindre enn 0,2 vekt% nikkel. 3.27 g of titanium oxycarbide containing 14.8 wt% oxygen and 11.5 wt% carbon and also 13 wt% nickel powder was pressed into a tablet and heated to 1700°C in a vacuum furnace and held at this temperature for 1.5 hours and then at 1900°C for a further 2 hours. The final pressure was 10<-1> mm Hg. After cooling, titanium metal was obtained which contained 7.5 wt% oxygen and 4.7 wt% carbon and less than 0.2 wt% nickel.
Eksempel XIII Example XIII
13,22 g vanadiumoksykarbid inneholdende 15,8 vekt% oksygen, 8,1 vekt% bundet karbon og 1,3 vekt% fritt karbon ble opphetet til 1440°C og holdt ved denne temperatur i 16 timer og deretter ved 1580°C i 4 timer ved et trykk på henholdsvis 13.22 g of vanadium oxycarbide containing 15.8 wt% oxygen, 8.1 wt% bound carbon and 1.3 wt% free carbon was heated to 1440°C and held at this temperature for 16 hours and then at 1580°C for 4 hours by pressing respectively
-5 -4 10 og 10 mm Hg. Det erholdte vanadium inneholdt etter kjøling 0,4 vekt% oksygen og mindre enn 0,1 vekt% karbon. -5 -4 10 and 10 mm Hg. The vanadium obtained contained, after cooling, 0.4% by weight of oxygen and less than 0.1% by weight of carbon.
De metalloksykarbider som ble anvendt i eksemplene XI-XIII var fremstilt ved at mån ledet metan over Nb-O,-, Ti0o og ^ 2°5 vec* en temPeratur mellom 1000 og 1200 C. The metaloxycarbides used in examples XI-XIII were prepared by passing methane over Nb-O,-, Ti0o and ^ 2°5 vec* at a temperature between 1000 and 1200 C.
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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NLAANVRAGE7202136,A NL172566C (en) | 1972-02-18 | 1972-02-18 | METHOD FOR PREPARING VANADIUM. |
NL7217490A NL175736C (en) | 1972-12-22 | 1972-12-22 | METHOD FOR PREPARING TITAN, NIOOB OR ALLOYS THEREOF. |
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NO135595B true NO135595B (en) | 1977-01-17 |
NO135595C NO135595C (en) | 1977-04-27 |
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CA (1) | CA1026101A (en) |
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FR (1) | FR2172367A1 (en) |
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- 1973-02-01 CA CA162,573A patent/CA1026101A/en not_active Expired
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DD102412A5 (en) | 1973-12-12 |
AT331046B (en) | 1976-07-26 |
NO135595C (en) | 1977-04-27 |
IT979212B (en) | 1974-09-30 |
FI56555C (en) | 1980-02-11 |
FR2172367B1 (en) | 1975-08-22 |
DE2307783B2 (en) | 1974-05-02 |
AU475793B2 (en) | 1976-09-02 |
CH592742A5 (en) | 1977-11-15 |
AU5226173A (en) | 1974-08-22 |
CA1026101A (en) | 1978-02-14 |
SE396617B (en) | 1977-09-26 |
JPS4897706A (en) | 1973-12-12 |
BE795533A (en) | 1973-08-16 |
FI56555B (en) | 1979-10-31 |
ES411699A1 (en) | 1976-01-01 |
DE2307783A1 (en) | 1973-08-30 |
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