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SE1300384A1 - Iron and tungsten-containing briquettes - Google Patents

Iron and tungsten-containing briquettes Download PDF

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Publication number
SE1300384A1
SE1300384A1 SE1300384A SE1300384A SE1300384A1 SE 1300384 A1 SE1300384 A1 SE 1300384A1 SE 1300384 A SE1300384 A SE 1300384A SE 1300384 A SE1300384 A SE 1300384A SE 1300384 A1 SE1300384 A1 SE 1300384A1
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Sweden
Prior art keywords
tungsten
powder
weight
briquettes
iron
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SE1300384A
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Swedish (sv)
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SE537464C2 (en
Inventor
Dag Sjöberg
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Ferrolegeringar Ab
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Publication date
Application filed by Ferrolegeringar Ab filed Critical Ferrolegeringar Ab
Priority to SE1300384A priority Critical patent/SE537464C2/en
Priority to TW103118375A priority patent/TW201501839A/en
Priority to EP14805161.8A priority patent/EP3003606A4/en
Priority to PCT/SE2014/050654 priority patent/WO2014193299A1/en
Publication of SE1300384A1 publication Critical patent/SE1300384A1/en
Publication of SE537464C2 publication Critical patent/SE537464C2/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C35/00Master alloys for iron or steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/001Starting from powder comprising reducible metal compounds
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/244Binding; Briquetting ; Granulating with binders organic
    • C22B1/245Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/30Obtaining chromium, molybdenum or tungsten
    • C22B34/36Obtaining tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/12Dry methods smelting of sulfides or formation of mattes by gases
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0235Starting from compounds, e.g. oxides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C35/00Master alloys for iron or steel
    • C22C35/005Master alloys for iron or steel based on iron, e.g. ferro-alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/006Starting from ores containing non ferrous metallic oxides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

19 SAMMANDRAG Uppfinningen avser jam- och volframhaltiga briketter samt en process for att framstalla brikettema. En rabrikett framstalls genom blandning av eft jampulver och ett volframhaltigt pulver, samt brikettering av blandningen. 19 SUMMARY The invention relates to jam- and tungsten-containing briquettes as well as a process for producing the briquettes. A briquette is prepared by mixing eft yam powder and a tungsten-containing powder, as well as briquetting the mixture.

Description

1 JARN- OCH VOLFRAMHALTIGA BRI(ETTER TEKNISKT OMRADE Foreliggande uppfinning avser en process for att framstalla jam- och volframhaltiga briketter. Uppfinningen avser aven briketter framstallda med processen. TECHNICAL FIELD The present invention relates to a process for producing jam- and tungsten-containing briquettes. The invention also relates to briquettes produced by the process.

BAKGRUND W011053231 redogor for en metod for att framstalla ett jam- och volframhaltigt pulver eller pulveragglomerat. Ett pulver innehallande volframkarbid blandas med ett 10 jarnoxidpulver och/eller ett pulver innehallande volframoxid och eventuellt ett jarnpulver. Blandningen varms upp i en neutral eller svagt reducerad atmosfar. BACKGROUND WO101053231 discloses a method of making a jam- and tungsten-containing powder or powder agglomerate. A powder containing tungsten carbide is mixed with an iron oxide powder and / or a powder containing tungsten oxide and optionally an iron powder. The mixture is heated in a neutral or slightly reduced atmosphere.

W02008091210 redogor for ett jarn- och volframhaltigt pulver innehallande 30-60 viktprocent W och resten jam. Pulvret framstalls genom att ett jarnpulver blandas med ett W03-pulver. En kula kan framstallas av pulvret. WO2008091210 describes an iron and tungsten-containing powder containing 30-60% by weight of W and the remainder jam. The powder is prepared by mixing an iron powder with a WO 3 powder. A ball can be made of the powder.

UPPFINNINGENS SYFTEN Det är ett andamal med uppfinningen att tillhandahalla ett nytt jam- och volframhaltigt material som lampar sig for volframtillsats i smaltindustrin, exempelvis stal-, gjuteri- och superlegeringsindustrin, samt en process for att framstalla sadant material pa ett jamforelsevis kostnadseffektivt sat. OBJECTS OF THE INVENTION It is an object of the invention to provide a new yarn and tungsten-containing material which is suitable for tungsten additive in the smelting industry, for example the steel, foundry and superalloy industry, and a process for producing such material in a comparatively cost-effective manner.

BESKRIVNING AV UPPFINNINGEN Minst ett av de ovannamnda syftena uppnas atminstone i viss utstrackning genom en 25 process for att framstalla jam- och volframhaltiga briketter innefattande momenten att: astadkomma en blandning innefattande (i viktprocent): 1-jarnpulver innehallande minst 80 % metalliskt jam, 2-97volframhaltigt pulver innehallande volframoxider och/eller volframkarbider, eventuellt 1-kolpulver, 2-90molybdenhaltigt pulver i blandningen tillsatta: en vatska, foretradesvis vatten, eventuellt ett eller flera av: bindemedel, 2 slaggbildare, avsvavlingsmedel, ) brikettera for att astadkomma ett flertal rabriketter Genom denna process är det mojligt att framstalla jam- och volframhaltiga rabriketter. DESCRIPTION OF THE INVENTION At least one of the above objects is achieved at least to some extent by a process for producing jam- and tungsten-containing briquettes comprising the steps of: producing a mixture comprising (in weight percent): 1-iron powder containing at least 80% metallic jam, 2 -97 tungsten-containing powder containing tungsten oxides and / or tungsten carbides, optionally 1-carbon powder, 2-90 molybdenum-containing powder added to the mixture: a liquid, preferably water, optionally one or more of: binder, 2 slag formers, desulfurizing agent, briquettes to produce a plurality of rhubarb Through this process, it is possible to produce jam- and tungsten-containing apricots.

De icke-reducerade rabriketterna kan anvandas som substitut for konventionellt framstallda jarn—volfram- ochleller jam—molybden-legeringar, vid legering av smdltan i industriproduktion. Rabriketterna kan framstallas till lagre kostnader an jdrnlegeringar av standardkvalitet. Deras porosa struktur underldttar snabb upplosning i en stalsmdlta. The non-reduced briquettes can be used as substitutes for conventionally produced iron-tungsten and / or yam-molybdenum alloys, in alloying the smelting agent in industrial production. The briquettes can be manufactured at lower costs than standard quality iron alloys. Their porous structure facilitates rapid dissolution in a steel melt.

Briketterna kan Ian transporteras pd ett transportband utan risk att rulla ay. The briquettes can be transported on a conveyor belt without the risk of rolling.

Vid beredning av blandningen är den totala kvantiteten tillsatt vatten cirka 110 viktprocent av blandningen, mest foredraget 2-5 viktprocent. When preparing the mixture, the total quantity of water added is about 110% by weight of the mixture, most preferably 2-5% by weight.

Foretradesvis anvands varken bindemedel eller slaggbildare. Ndr det jarnhaltiga pulvret blandas i van tillstand forstarker det briketterna, vilket gör anvandning av bindemedel onodig. Darmed kan kvantiteten fororeningar minskas. Preferably, neither binder nor slag former is used. When the ferrous powder is mixed in the usual state, it strengthens the briquettes, which makes the use of binders unnecessary. Thus, the quantity of pollutants can be reduced.

Eventuellt omfattar metoden momentet att: a) torka rabriketterna. The method may include the step of: a) drying the briquettes.

Genom att fabriketterna torkas minimeras risken for sprickbildning pd grund av snabb forangning av vatskan ndr de varms upp vid hoga temperaturer. By drying the factories, the risk of cracking is minimized due to rapid evaporation of the liquid when they are heated at high temperatures.

Foretradesvis omfattar det eventuella torkningsmomentet minst ett av foljande: torkning av fabriketterna till en fukthalt under 5 viktprocent, foretradesvis under 3 viktprocent, torkning av rabriketterna vid en temperatur i intervallet 50-250 °C, foretradesvis 80-200 °C, mer foredraget 100-150 °C. Preferably, the optional drying step comprises at least one of the following: drying the fabric to a moisture content below 5% by weight, preferably below 3% by weight, drying the fabric at a temperature in the range of 50-250 ° C, preferably 80-200 ° C, more preferably 100- 150 ° C.

Vid torkning av briketterna sker en temperaturokning awn ndr ingen extern varme anvands. Detta tros bero pd reaktioner nar jarnet oxiderar. Aven briketternas hallfasthet okar. Det gOr det mofligt att tillhandahalla tillrackligt starka briketter utan behov av att tillsatta bindemedel, d.v.s. jampulvret ersatter behovet av bindemedel. Aven dammproblem minimeras. 3 Manga olika typer av industritorkar kan anvandas. Briketterna kan aven torkas utan aktiv uppvarmning, exempelvis i omgivningstemperatur. I en tork kan anga avlagsnas med en gasanga eller med vakuum. For forbattrad processekonomi är torktiden i en tork foretradesvis i intervallet -1minuter, mer foredraget 20-60 minuter. Men langre torktider är givetvis tankbara. When drying the briquettes, a temperature increase occurs when no external heat is used. This is thought to be due to reactions when the iron oxidizes. The half-strength of the briquettes also increases. This makes it possible to provide sufficiently strong briquettes without the need to add binders, i.e. the jam powder replaces the need for binder. Dust problems are also minimized. 3 Many different types of industrial dryers can be used. The briquettes can also be dried without active heating, for example at ambient temperature. In a dryer, the steam can be removed with a gas steam or with a vacuum. For improved process economy, the drying time in a dryer is preferably in the range of -1 minutes, more preferably 20-60 minutes. But longer drying times are of course conceivable.

Fukthalten definieras som den kvantitet vatten som finns i rabriketterna utover kristallvatten. Fukthalten kan faststallas genom en analys av typen LOD (Loss On Drying, fOrlust vid torkning) i enlighet med ASTM D2216-10. The moisture content is defined as the quantity of water present in the briquettes in addition to crystal water. The moisture content can be determined by an analysis of the LOD (Loss On Drying) type in accordance with ASTM D2216-10.

Torrsubstanssammansattningen avser sammansattningen for ett torkat exemplar, d.v.s. exklusive eventuell fukt som finns i rabriketterna. The dry matter composition refers to the composition of a dried specimen, i.e. excluding any moisture present in the briquettes.

Foretradesvis omfattar metoden momentet att: b) reducera rabriketterna for att astadkomma ett flertal reducerade briketter. Preferably, the method comprises the step of: b) reducing the briquettes to produce a plurality of reduced briquettes.

Foretradesvis omfattar reduktionsmomentet minst ett av foljande: reduktion vid en temperatur i intervallet 800-1 500 °C, foretradesvis 1 050- 1 400 °C, mer fOredraget 1 100-1 300 °C, mest fOredraget 1 150-1 250 °C, reduktion under minst 20 minuter, mer fOredraget minst 30 minuter, - reduktion i en ugn matad med en inert eller reducerande gas, foretradesvis matad med en svagt reducerande gas, reduktion vid ett arbetstryck i intervallet 0,1-5 atm, foretradesvis 0,8-2 atm, mer fOredraget 1,05-1,2 atm. Preferably, the reduction moment comprises at least one of the following: reduction at a temperature in the range 800-1 500 ° C, preferably 1,050-1,400 ° C, more preferably 1,100-1,300 ° C, most preferably 1,150-1,250 ° C, reduction for at least 20 minutes, more preferably at least 30 minutes, - reduction in an oven fed with an inert or reducing gas, preferably fed with a weakly reducing gas, reduction at a working pressure in the range 0.1-5 atm, preferably 0.8 -2 atm, more lecture 1.05-1.2 atm.

Genom overvakning av bildandet av CO/CO2 kan det faststallas nar reduktionsprocessen är avslutad. Reduktionstiden kan optimeras genom att bildandet av CO och CO2 mats, i synnerhet CO eftersom CO2 bildas huvudsakligen under de forsta minuterna av reduktionen varefter CO-bildandet dominerar tills kolkallan är forbrukad eller alla reducerbara oxider har reducerats. Foretradesvis är reduktionstiden hogst timmar, foretradesvis hogst 2 timmar, mer fOredraget hogst 1 timme. Beroende pa reduktionstiden, reduktionstemperaturen och forhallandet mellan kol och reducerbara oxider i briketterna kan briketternas reducerbara oxider reduceras delvis eller fullstandigt. By monitoring the formation of CO / CO2, it can be determined when the reduction process is completed. The reduction time can be optimized by feeding the formation of CO and CO2, in particular CO because CO2 is formed mainly during the first minutes of the reduction after which the CO formation dominates until the carbon dioxide is consumed or all reducible oxides have been reduced. Preferably the reduction time is at most hours, preferably at most 2 hours, more preferably at most 1 hour. Depending on the reduction time, the reduction temperature and the ratio between carbon and reducible oxides in the briquettes, the reducible oxides of the briquettes can be partially or completely reduced.

Atmosfaren inuti ugnen regleras foretradesvis genom att en inert eller en reducerande gas, foretradesvis en svagt reducerande gas, matas in i en ande av ugnen, och att gaser (exempelvis reaktionsgaser (exempelvis CO, CO2, och H2O) och den inmatade gasen) 4 evakueras i den motsatta anden, mer foredraget genom att den inerta eller reducerande gasen matas in motstroms vid en utloppssida av ugnen, och att gaser evakueras vid en inloppssida av ugnen. Det betyder att den inerta eller reducerande gasen fOretradesvis matas motstroms. Den inerta gasen eller en reducerande gas kan exempelvis vara argon, N2, H2 eller valfri blandning av H2/N2 (exempelvis i forhallandet 5:95 med avseende pa volym). The atmosphere inside the furnace is preferably controlled by feeding an inert or a reducing gas, preferably a weakly reducing gas, into one spirit of the furnace, and evacuating gases (for example reaction gases (for example CO, CO2, and H 2 O) and the feed gas) in the opposite spirit, more preferably in that the inert or reducing gas is fed countercurrently at an outlet side of the furnace, and that gases are evacuated at an inlet side of the furnace. This means that the inert or reducing gas is preferably fed countercurrently. The inert gas or a reducing gas may be, for example, argon, N2, H2 or any mixture of H2 / N2 (for example in a ratio of 5:95 by volume).

Reduktionsugnen är foretradesvis en genommatningsugn men kan aven vara en satsugn. I en genommatningsugn transporteras briketterna fran ett inlopp till ett utlopp under reduktionen. Exempel pa ugnar är exempelvis roterugnar, roterhardugnar, schaktugnar, rostugnar, rorliga rostugnar, tunnelugnar eller satsugnar. Aven andra typer av ugnar som anvands vid direktreduktion av metalloxider i fast tillstand kan anvandas. I en foredragen utforingsform anvands en ugn med transportband. The reduction furnace is preferably a feed-through furnace but can also be a batch furnace. In a feed-through oven, the briquettes are transported from an inlet to an outlet during the reduction. Examples of kilns are, for example, rotary kilns, rotary kilns, shaft kilns, roasting kilns, mobile roasting kilns, tunnel kilns or batch kilns. Other types of furnaces used in the direct reduction of solid state metal oxides can also be used. In a preferred embodiment, an oven with a conveyor belt is used.

FOretradesvis arbetar reduktionsugnen vid ett tryck i intervallet 0,1-5 atm, foretradesvis 0,8-2 atm, mer foredraget vid ett tryck i intervallet 1,0-1,5 atm, mest foredraget 1,051,2 atm. Preferably, the reduction furnace operates at a pressure in the range of 0.1-5 atm, preferably 0.8-2 atm, more preferably at a pressure in the range of 1.0-1.5 atm, most preferably 1.051.2 atm.

Atmosfaren inuti ugnen regleras foretradesvis genom att en inert eller en reducerande gas, foretradesvis en svagt reducerande gas, matas in i en ande av ugnen och gaser (exempelvis reaktionsgaser (exempelvis CO, CO2, och H20) och den inmatade gasen) evakueras i den motsatta anden, mer foredraget genom att den inerta eller reducerande gasen matas in motstroms vid utloppssidan av ugnen, och att gaser evakueras vid inloppssidan av ugnen. Det betyder aft den inerta eller reducerande gasen foretradesvis matas motstroms. Den inerta gasen eller en reducerande gas kan exempelvis vara argon, N2, H2 eller valfri blandning av H2/N2 (exempelvis i forhallandet 5:95 med avseende pa volym). The atmosphere inside the furnace is preferably controlled by feeding an inert or a reducing gas, preferably a weakly reducing gas, into one spirit of the furnace and gases (for example reaction gases (for example CO, CO2, and H 2 O) and the feed gas) are evacuated in the opposite spirit, more preferably by feeding the inert or reducing gas in countercurrent at the outlet side of the furnace, and evacuating gases at the inlet side of the furnace. This means that the inert or reducing gas is preferably fed countercurrently. The inert gas or a reducing gas may be, for example, argon, N2, H2 or any mixture of H2 / N2 (for example in a ratio of 5:95 by volume).

Foretradesvis omfattar metoden vidare momentet att: c) kyla de reducerade briketterna i en icke-oxiderande atmosfar (exempelvis reducerande eller inert) till en temperatur under 200 °C, mer foredraget under 150 °C, foretradesvis i en inert atmosfar. Preferably, the method further comprises the step of: c) cooling the reduced briquettes in a non-oxidizing atmosphere (eg reducing or inert) to a temperature below 200 ° C, more preferably below 150 ° C, preferably in an inert atmosphere.

Atmosfaren under kylning kan exempelvis vara argon, N2, H2 eller valfri blandning av H21181-2 (exempelvis i forhallandet 5:95 med avseende pa volym). Alien andra atmosfarer kan anvandas. Om det är onskvart att ha mycket laga nivaer av kvave i briketterna, kan briketterna kylas i en kvavefri atmosfar sasom exempelvis en argongasatmosfar. The atmosphere during cooling can be, for example, argon, N2, H2 or any mixture of H21181-2 (for example in the ratio 5:95 with respect to volume). Alien other atmospheres can be used. If it is undesirable to have very low levels of nitrogen in the briquettes, the briquettes can be cooled in a nitrogen-free atmosphere such as an argon gas atmosphere.

I en utforingsform utfors brikettering vid ett briketteringstryck i intervallet 80- 1 000 kg/cm2, foretradesvis 100-500 kg/cm2. In one embodiment, briquetting is performed at a briquetting pressure in the range of 80-1000 kg / cm2, preferably 100-500 kg / cm2.

I en utforingsform utfors brikettering vid ett briketteringstryck i intervallet 1 00010 000 kg/cm2, foretradesvis 2 000-5 000 kg/cm2. In one embodiment, briquetting is performed at a briquetting pressure in the range of 1,00010,000 kg / cm 2, preferably 2,000-5,000 kg / cm 2.

Foretradesvis är briketteringsmaskinen en valspress. Emellertid kan andra typer av briketteringsmaskiner anvandas. Preferably, the briquetting machine is a roller press. However, other types of briquetting machines can be used.

Eventuellt varmebehandlas rabriketterna vid en lagre temperatur fore reduktion. Foretradesvis varmebehandlas rabriketterna vid en temperatur i intervallet 200-800 °C, mer fOredraget 400-700 °C. Foretradesvis sker den eventuella varmebehandlingen vid lagre temperatur fran 10 minuter till mindre an 2 timmar, foretradesvis mindre an 1 timme. Genom varmebehandling vid lagre temperaturer kan det eventuella smorjmedlet (om sadant finns) brannas bort pa ett kontrollerat sat. Dessutom kan molybdentrioxid (om sadan finns) reduceras till molybdendioxid. Detta kan anvandas som ett forreduktionsmoment fore den reduktion som beskrivs i foregaende stycke eller vid framstallning av delvis reducerade briketter. Den eventuella varmebehandlingen vid 200-800 °C kan utforas i samma ugn som reduktionen. Den eventuella varmebehandlingen och den eventuella torkningen kan ocksa. kombineras. The briquettes may be heat-treated at a lower temperature before reduction. Preferably, the briquettes are heat-treated at a temperature in the range of 200-800 ° C, more preferably 400-700 ° C. Preferably, the possible heat treatment takes place at a lower temperature from 10 minutes to less than 2 hours, preferably less than 1 hour. By heat treatment at lower temperatures, any lubricant (if any) can be burned off in a controlled manner. In addition, molybdenum trioxide (if present) can be reduced to molybdenum dioxide. This can be used as a pre-reduction step before the reduction described in the preceding paragraph or in the production of partially reduced briquettes. The possible heat treatment at 200-800 ° C can be carried out in the same oven as the reduction. The possible heat treatment and the possible drying can also. combined.

Eventuellt kan smorjmedel och/eller bindemedel och/eller slaggbildare ochleller avsvavlingsmedel tillsattas under blandningen. De eventuella bindemedlen kan vara organiska eller oorganiska bindemedel. Bindemedlen kan exempelvis vara ett kolhaltigt bindemedel som delvis ersatter det kolhaltiga pulvret. Andra bindemedel kan exempelvis vara bentonit och/eller dextrin och/eller natriumsilikat och/eller kalk. Den eventuella slaggbildaren kan vara kalksten, dolomit och/eller olivin. Den totala kvantiteten smorjmedel och/eller bindemedel och/eller slaggbildare och/eller avsvavlingsmedel kan vara 0,1-10 viktprocent av rabrikettens torrsubstanshalt, mer foredraget mindre an 5 viktprocent. Den kan vara i intervallet 1-10 viktprocent. Bindemedlen är valfria eftersom rabriketterna genom tillsats av vattnet och jarnet blir tillrackligt starka for att reduceras i reduktionsugnen utan allvarlig sprickbildning. Om smorjmedel tillsatts, tillfors det foretradesvis i kvantiteterna 0,1-2 procent av brikettens ton-substanshalt, exempelvis cirka 0,5-1 viktprocent. Smorjmedlet kan exempelvis vara zinkstearat. Emellertid kan andra smorjmedel som anvands i pulvermetallurgi tillsattas. 6 Beroende pa pulvrets renhet kan briketternas blandning innehalla ytterligare komponenter inklusive oxider som är svara att reducera. Kvantiteten av sadana komponenter bestams huvudsakligen av renheten hos det volframhaltiga pulvret och det eventuella molybdenhaltiga pulvret, men kan aven komma fran fororeningar i jarnpulvret, kolpulvret och fran reaktioner med komponenter i den omgivande atmosfaren under uppvarmning, reduktion eller kylning Den Overgripande processen är endoterm och kraver varme. FOr att minska mangden extern varme som kravs kan syrgas eller luft tillhandahallas i en forvarmningszon for att reagera med den bildade kolmonoxiden sâ att det bildas koldioxidgas. Om luft anvands kan briketternas kvaveupptag Oka. Med hjalp av syre kan kvaveupptaget under uppvarmnings- och reduktionsmomentet minimeras. Optionally, lubricants and / or binders and / or slag formers and / or desulfurizing agents may be added during mixing. The possible binders can be organic or inorganic binders. The binders may, for example, be a carbonaceous binder which partially replaces the carbonaceous powder. Other binders may be, for example, bentonite and / or dextrin and / or sodium silicate and / or lime. The possible slag former may be limestone, dolomite and / or olivine. The total quantity of lubricant and / or binder and / or slag-forming agent and / or desulfurizing agent may be 0.1-10% by weight of the dry matter content of the bricks, more preferably less than 5% by weight. It can be in the range 1-10% by weight. The binders are optional because the additives by adding the water and the iron become sufficiently strong to be reduced in the reduction furnace without severe cracking. If lubricant is added, it is preferably supplied in the quantities of 0.1-2 percent of the tonnage content of the briquette, for example about 0.5-1% by weight. The lubricant may, for example, be zinc stearate. However, other lubricants used in powder metallurgy may be added. Depending on the purity of the powder, the briquette mixture may contain additional components including oxides which are responsible for reducing. The quantity of such components is mainly determined by the purity of the tungsten-containing powder and any molybdenum-containing powder, but may also come from impurities in the iron powder, carbon powder and from reactions with components in the ambient atmosphere during heating, reduction or cooling. The overall process is endothermic and heat. To reduce the amount of external heat required, oxygen or air may be provided in a preheating zone to react with the carbon monoxide formed to form carbon dioxide gas. If air is used, the briquettes' nitrogen uptake can increase. With the help of oxygen, nitrogen uptake during the heating and reduction operation can be minimized.

I stallet fOr att rabriketterna torkas innan de fcirs in i reduktionsugnen kan ugnen ha en torkzon som arbetar vid en temperatur i intervallet 80-200 °C, foretradesvis 100-150 °C. Reduktionsugnen kan aven omfatta en forreduktionszon, nedstroms frail torkzonen om sadan anvands, och arbeta i intervallet 200-800 °C, foretradesvis 400-700 °C. Instead of the briquettes being dried before being fed into the reduction oven, the oven may have a drying zone operating at a temperature in the range of 80-200 ° C, preferably 100-150 ° C. The reduction furnace may also comprise a pre-reduction zone, downstream of the drying zone if used, and operate in the range 200-800 ° C, preferably 400-700 ° C.

De jam- och volframhaltiga rabriketterna har en torrsubstanssammansattning, i viktprocent, av: a) 90-100 av en blandning innefattande, i viktprocent av blandningen: 2-97volframhaltigt pulver innehallande volframoxider och/eller volframkarbider, eventuellt 0,1-25 2-90 resten 1- b) eventuellt FOretradesvis bestar de reducerade jam- och volframhaltiga briketterna av, i viktprocent: 7 3-97 Mo + W50-97 < < Si< Co< Andra amnen< och resten Fe 2-40. The jam- and tungsten-containing briquettes have a dry matter composition, in weight percent, of: a) 90-100 of a mixture comprising, in weight percent of the mixture: 2-97 tungsten-containing powder containing tungsten oxides and / or tungsten carbides, optionally 0.1-25 2-90 residue 1- b) optionally Preferably, the reduced jam and tungsten-containing briquettes consist of, in weight percent: 7 3-97 Mo + W50-97 <<Si <Co <Other substances <and the rest Fe 2-40.

Brikettema kan ersatta konventionellt tillverkade jamlegeringar, vid legering med volfram och eventuellt volfram/molybden vid smaltforfaranden. Brikettema kan framstallas till lagre kostnader an jam—volfram av standardkvalitet. Brikettema loses upp snabbare an jam—volfram av standardkvalitet. Beroende pa reduktionstiden, den relativa kvantiteten kol i relation till kvantiteten reducerbara oxider och reduktionstemperaturen kan syrehalten i brikettema minskas delvis eller fullstandigt. The briquettes can replace conventionally manufactured jam alloys, in the case of alloying with tungsten and possibly tungsten / molybdenum in smelting processes. The briquettes can be manufactured at lower cost than standard quality jam-tungsten. The briquettes dissolve faster than standard-quality jam-tungsten. Depending on the reduction time, the relative quantity of carbon in relation to the quantity of reducible oxides and the reduction temperature, the oxygen content of the briquettes can be reduced partially or completely.

Brikettema kan latt transporteras pa ett transportband utan risk att rulla ay. The briquettes can be easily transported on a conveyor belt without risk of rolling.

Genom brikettering fOre reduktion är det mojligt att framstalla en brikett som har hogre porositet an en brikett bildad av reducerade pulver. Dessutom är det mojligt att framstalla en brikett som är fri frail bindemedel och smorjmedel. By briquetting before reduction, it is possible to produce a briquette which has a higher porosity than a briquette formed of reduced powders. In addition, it is possible to produce a briquette that is free frail binder and lubricant.

Blandning Den blandning som tillhandahalls i moment a) innefattar (i viktprocent): 2-97volframhaltigt pulver, eventuellt 0,1-kolpulver, 2-90molybdenhaltigt pulver, resten 1-jampulver. Mixture The mixture provided in step a) comprises (in% by weight): 2-97 tungsten-containing powder, optionally 0.1-carbon powder, 2-90 molybdenum-containing powder, the remainder 1-jam powder.

Foretradesvis utgor jampulvret 2-25 viktprocent, mer foredraget 3-15 viktprocent. Preferably the jam powder is 2-25% by weight, more preferably 3-15% by weight.

Foretradesvis utgor det volframhaltiga pulvret minst 20 viktprocent. 8 Foretradesvis utgor det volframhaltiga pulvret + det molybdenhaltiga pulvret mer an viktprocent av blandningen, mer foredraget mer an 70 viktprocent av blandningen. Preferably, the tungsten-containing powder is at least 20% by weight. Preferably the tungsten-containing powder + the molybdenum-containing powder constitutes more than a percentage by weight of the mixture, more preferably more than 70% by weight of the mixture.

I en utforingsform bestar blandningen av (i viktprocent): 1-40, foretradesvis 3-15, av ett jampulver, och 75-99, foretradesvis 85-97, av ett volframhaltigt pulver. In one embodiment, the mixture consists of (in weight percent): 1-40, preferably 3-15, of a yam powder, and 75-99, preferably 85-97, of a tungsten-containing powder.

Foretradesvis innehaller det volframhaltiga pulvret volframoxider och volframkarbider. Foretrddesvis är de reducerbara oxidema i det volframhaltiga pulvret och jampulvret stokiometriskt anpassade efter kolet i volframkarbidema, sa att kolhalten efter en reduktion utgor mindre an 10 viktprocent, foretradesvis mindre an 5 viktprocent, mer foredraget mindre an 1 viktprocent, mest foredraget mindre an 0,5 viktprocent; och syret utgOr mindre an 10 viktprocent, foretradesvis mindre an 5 viktprocent, mest foredraget mindre an 3 viktprocent. Preferably, the tungsten-containing powder contains tungsten oxides and tungsten carbides. Preferably the reducible oxides in the tungsten-containing powder and the jam powder are stoichiometrically adapted to the carbon in the tungsten carbides, so that the carbon content after a reduction is less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, most preferably less than 0.5 weight percent; and the oxygen is less than 10% by weight, preferably less than 5% by weight, most preferably less than 3% by weight.

Darigenom kan jam- och volframhaltiga briketter framstallas, som vasentligen bestar av jam och volfram samt oundvikliga fororeningar. Thereby, jam- and tungsten-containing briquettes can be produced, which essentially consist of jam and tungsten as well as unavoidable contaminants.

Jam- och volframhaltiga briketter som bestar av jam och volfram samt oundvikliga fororeningar kan aven framstallas av en blandning ddr volframkarbider delvis eller till fullo är ersatta av ett kolpulver, d.v.s. sa att kolet i volframkarbider och/eller kolpulver stokiometriskt motsvarar de reducerbara oxidema i det volframhaltiga pulvret och jampulvret. Jam and tungsten-containing briquettes consisting of jam and tungsten as well as unavoidable impurities can also be produced from a mixture of tungsten carbides which are partially or completely replaced by a carbon powder, i.e. said that the carbon in tungsten carbides and / or carbon powders stoichiometrically corresponds to the reducible oxides in the tungsten-containing powder and the jam powder.

Jam- och volframhaltiga briketter som bestar av jam, volfram och molybden samt oundvikliga fororeningar kan framstallas av blandningen genom tillsats av det eventuella molybdenhaltiga pulvret. Har anpassas kolet fran volframkarbidema och/eller kolpulvret stokiometriskt efter de reducerbara oxidema i det molybdenhaltiga pulvret, det volframhaltiga pulvret och jampulvret. Har är foretradesvis det volframhaltiga pulvret ett volframkarbidpulver innefattande minst 70 viktprocent WC, foretradesvis minst 95 viktprocent WC, eller ett volframoxidpulver innefattande minst 70 viktprocent W03, foretradesvis minst 95 viktprocent W03, eller en blandning av dessa pulver. Jam- and tungsten-containing briquettes consisting of jam, tungsten and molybdenum as well as unavoidable impurities can be prepared from the mixture by adding any molybdenum-containing powder. Has the carbon from the tungsten carbides and / or the carbon powder been adapted stoichiometrically to the reducible oxides in the molybdenum-containing powder, the tungsten-containing powder and the jam powder. Preferably, the tungsten-containing powder is a tungsten carbide powder comprising at least 70% by weight of WC, preferably at least 95% by weight of WC, or a tungsten oxide powder comprising at least 70% by weight of WO 3, preferably at least 95% by weight of WO 3, or a mixture of these powders.

Foretradesvis balanseras kolet och syret sa att kolhalten efter reduktion utgor mindre an viktprocent, foretradesvis mindre an 5 viktprocent, mer foredraget mindre an 1 viktprocent, mest foredraget mindre an 0,5 viktprocent; och syret utgor mindre an 9 viktprocent, foretradesvis mindre an 5 viktprocent, mest foredraget mindre an 3 viktprocent. Preferably the carbon and oxygen are balanced so that the carbon content after reduction is less than a percentage by weight, preferably less than 5% by weight, more preferably less than 1% by weight, most preferably less than 0.5% by weight; and the oxygen is less than 9% by weight, preferably less than 5% by weight, most preferably less than 3% by weight.

De relativa kvantiteterna molybden och volfram kan varieras genom forandring av de relativa kvantitetema av det volframhaltiga pulvret och det molybdenhaltiga pulvret, samtidigt som hansyn tas till kol- och syrebalansen. The relative quantities of molybdenum and tungsten can be varied by changing the relative quantities of the tungsten-containing powder and the molybdenum-containing powder, while taking into account the carbon and oxygen balance.

I en foredragen utforingsform är viktforhallandet mellan volframkarbid och volframoxid (WC/W03) Mom intervallet 0,5-5, foretradesvis 1-4, mer foredraget 1,5-3. En optimal 10 balans är cirka 2. Darigenom kan volframkarbiden motsvara volframoxiden utan behov av tillsats av kolpulver. In a preferred embodiment, the weight ratio of tungsten carbide to tungsten oxide (WC / WO 3) is in the range 0.5-5, preferably 1-4, more preferably 1.5-3. An optimal balance is about 2. As a result, the tungsten carbide can correspond to the tungsten oxide without the need for the addition of carbon powder.

I en utforingsform bestams viktforhallandet mellan molybden och volfram (Mo/W) till att vara Mom intervallet 0,25-4, fciretradesvis 0,5-2, mer foredraget 0,8-1,25. In one embodiment, the weight ratio of molybdenum to tungsten (Mo / W) is determined to be the Mom range of 0.25-4, preferably 0.5-2, more preferably 0.8-1.25.

Volframhaltigt pulver Det volframhaltiga pulvret är fOretradesvis nagot av: ett volframkarbidhaltigt pulver, ett volframoxidhaltigt pulver, en blandning av volframkarbidhaltigt pulver och volframoxidhaltigt pulver. Tungsten-containing powder The tungsten-containing powder is preferably any of: a tungsten-carbide-containing powder, a tungsten-oxide-containing powder, a mixture of tungsten-carbide-containing powder and tungsten-oxide-containing powder.

Volframkarbidhaltigt pulver Det volframkarbidhaltiga pulvret är ett pulver som innefattar volframkarbider inneslutna i en metallmatris. Foretradesvis erhalls det volframkarbidhaltiga pulvret fran hardmetallskrot med volfram. Det volframkarbidhaltiga pulvret innefattar foretradesvis 1-10 viktprocent kol, resten volfram och oavsiktliga fororeningar. Det volframkarbidhaltiga pulvret kan alien omfatta legeringskomponenter vilka har bildat en matris (bindande material) for hardmetallmaterialet med volfram. Proportionen av karbidfas är i allmanhet 70-97 % av kompositens totala vikt. Kolet ingar i pulverpartiklarna i form av volframkarbidkorn, och kornstorleken är vanligen i genomsnitt mellan 0,10 tm och 15 tm. Varje pulverpartikel kan innehalla flera volframkarbidkorn, i synnerhet om partiklarna dr stora. Vidare kan det volframkarbidhaltiga pulvret innehalla pulverpartiklar som är fria flan volframkarbidkorn; emellertid kommer de fiesta av pulverpartiklarna att innehalla ett eller flera korn av volframkarbid. Tungsten carbide-containing powder The tungsten carbide-containing powder is a powder comprising tungsten carbides enclosed in a metal matrix. Preferably, the tungsten carbide-containing powder is obtained from carbide scrap with tungsten. The tungsten carbide-containing powder preferably comprises 1-10% by weight of carbon, the remainder tungsten and unintentional impurities. The tungsten carbide-containing powder may alien comprise alloy components which have formed a matrix (binding material) for the cemented carbide material with tungsten. The proportion of carbide phase is generally 70-97% of the total weight of the composite. The carbon ingests in the powder particles in the form of tungsten carbide grains, and the grain size is usually on average between 0.10 tm and 15 tm. Each powder particle may contain several tungsten carbide grains, especially if the particles are large. Furthermore, the tungsten carbide-containing powder may contain powder particles which are free of tungsten carbide grains; however, most of the powder particles will contain one or more grains of tungsten carbide.

Vissa volframkarbidpulver kan innehalla kobolt upp till 15 viktprocent, vanligen runt 110 viktprocent Co. Exempelvis innehaller verktygsmaterialet i kretskortsborrar vanligen finkomiga hardmetaller med volfram som finns i en koboltmatris, vars kvantitet representerar 6 procent av verktygsmaterialets totala vikt, medan groykomiga hardmetaller med volfram vanligen am/ands for verktygsmaterialet till gruvborrar, dar kobolthalten i hardmetallmaterialet är cirka 10 viktprocent. Dessa pulver kan anvandas om kobolt kan tillatas eller onskas i den brikett som ska framstallas. I annat fall kan dessa pulver anvandas efter att ha urlakats pa kobolt. Exempelvis kan ett kommersiellt tillgangligt volframkarbidhaltigt pulver fran skrot som innehaller 1-10 viktprocent Co, vanligen i kvantiteter av 3-8 viktprocent Co, urlakas hydrometallurgiskt for att minska kobolthalten till mindre an 1 viktprocent Co, foretradesvis mindre an 0,5 viktprocent Co, mer fOredraget mindre an 0,2 viktprocent Co. Kobolt fran urlakningsprocessen kan atervinnas och nyttj as som en kommersiell pro dukt i sig. Some tungsten carbide powders may contain cobalt up to 15% by weight, usually around 110% by weight Co. For example, the tool material in circuit board drills usually contains fine hard carbide metals with tungsten contained in a cobalt matrix, the quantity of which represents 6 percent of the total weight of the tool material, while coarse grained hard metals with tungsten usually comprise the tool material for mining drills. These powders can be used if cobalt can be allowed or desired in the briquette to be produced. Otherwise, these powders can be used after leaching on cobalt. For example, a commercially available tungsten carbide-containing powder from scrap containing 1-10% by weight of Co, usually in quantities of 3-8% by weight of Co, can be leached hydrometallurgically to reduce the cobalt content to less than 1% by weight of Co, preferably less than 0.5% by weight of Co, more The preference is less than 0.2% by weight of Co. Cobalt from the leaching process can be recovered and used as a commercial product in itself.

Givetvis kan ett volframkarbidpulver som redan har lag halt eller är fritt fran kobolt anvandas. Of course, a tungsten carbide powder which is already low in content or free of cobalt can be used.

Det ror sig om ett pulver som innehaller mindre an 1 viktprocent Co, mer foredraget mindre an 0,5 viktprocent Co, annu mer foredraget mindre an 0,2 viktprocent Co. It is a powder which contains less than 1% by weight of Co, more preferably less than 0.5% by weight of Co, more preferably less than 0.2% by weight of Co.

Foretradesvis innehaller volframkarbidpulvret minst 90 viktprocent WC, mer foredraget minst 95 viktprocent. Preferably the tungsten carbide powder contains at least 90% by weight of WC, more preferably at least 95% by weight.

Foretradesvis passerar minst 90 viktprocent, mer foredraget minst 99 viktprocent, av partiklama i det volframkarbidhaltiga pulvret genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 250 lam, mer foredraget 125 jim, mest foredraget 90 lam. Mycket Lint pulver dar minst 99 viktprocent passerar genom en 45 lam testsikt kan lampligen anvandas. Preferably at least 90% by weight, more preferably at least 99% by weight, of the particles in the tungsten carbide-containing powder pass through a test screen in accordance with ISO 3310-1: 2000 with a nominal neck size of 250 lam, more preferably 125 μm, most preferably 90 lam. A lot of Lint powder where at least 99% by weight passes through a 45 lam test screen can be suitably used.

Volframoxidhaltigt pulver Det volframoxidhaltiga pulvret kan vara ett jam- och volframoxidhaltigt pulver, mer foredraget jamvolframat i form av mineralet ferberit. Foretradesvis en ferberit som innehaller over 60 % W03, mer foredraget minst 70 % W03. Ferberiten krossas och/eller mats oclVeller smulas ned till ett pulver sâ att minst 80 viktprocent av partiklarna, foretradesvis minst 90 %, passerar genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 250 itm, mer foredraget 125 jim. 11 Det volframoxidhaltiga pulvret kan alien vara ett rent volframoxidpulver innehallande mindre an 5 viktprocent andra amnen utover W och 0, foretradesvis mindre an 1 viktprocent andra amnen. Exempelvis ett pulver som innehaller minst 95 viktprocent W03, foretradesvis minst 99 viktprocent. Tungsten oxide-containing powder The tungsten oxide-containing powder may be a jam- and tungsten oxide-containing powder, more preferably jam-tungstate in the form of the mineral ferberite. Preferably a ferberite containing more than 60% WO 3, more preferably at least 70% WO 3. The ferberite is crushed and / or fed and / or crushed into a powder so that at least 80% by weight of the particles, preferably at least 90%, pass through a test sieve in accordance with ISO 3310-1: 2000 with a nominal neck size of 250 .mu.m, more preferably 125 .mu.m. The tungsten oxide-containing powder may alien be a pure tungsten oxide powder containing less than 5% by weight of other substances in addition to W and 0, preferably less than 1% by weight of other substances. For example, a powder containing at least 95% by weight of WO 3, preferably at least 99% by weight.

FOretradesvis passerar minst 80 viktprocent, mer fOredraget minst 90 viktprocent, av partiklama i volframoxidpulvret genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 2mer foredraget 125 jim, mest foredraget 90 lam. Mycket fint pulver dar minst 99 viktprocent passerar genom en 45 jim testsikt kan lampligen 10 anvandas. Preferably at least 80% by weight, more preferably at least 90% by weight, of the particles in the tungsten oxide powder pass through a test screen in accordance with ISO 3310-1: 2000 with a nominal neck size of 2 more preferably 125 μm, most preferably 90 lam. Very fine powder where at least 99% by weight passes through a 45 μm test sieve can suitably be used.

Det volframoxidhaltiga pulvret kan aven vara en blandning av jamvolframat och rent volframoxidpulver. The tungsten oxide-containing powder may also be a mixture of jam tungstate and pure tungsten oxide powder.

Aven andra tillgangliga kvaliteter av volframoxidpulver kan anvandas. Other available grades of tungsten oxide powder can also be used.

Molybdenhaltigt pulver Det molybdenhaltiga pulvret är fOretradesvis ett molybdenoxidpulver. Pulvret bestar foretradesvis av molybdendioxid- och/eller molybdentrioxidpulver. Molybdenum-containing powder The molybdenum-containing powder is preferably a molybdenum oxide powder. The powder preferably consists of molybdenum dioxide and / or molybdenum trioxide powder.

Molybdenoxidpulvret bar innehalla 50-80 viktprocent Mo, varvid ovriga komponenter är syre och fororeningar. Foretradesvis utgor fororeningarna mindre an 10 viktprocent, mer Riredraget mindre an 5 viktprocent, mest foredraget mindre an 1 viktprocent. The molybdenum oxide powder should contain 50-80% by weight of Mo, the other components being oxygen and impurities. Preferably the impurities are less than 10% by weight, more Rire draget less than 5% by weight, most preferably less than 1% by weight.

Foretradesvis passerar minst 90 viktprocent, mer foredraget minst 99 viktprocent, av partiklama i molybdenoxidpulvret genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 2mer foredraget 1mest foredraget 45 1,im. Preferably, at least 90% by weight, more preferably at least 99% by weight, of the particles in the molybdenum oxide powder pass through a test screen in accordance with ISO 3310-1: 2000 with a nominal neck size of 2 more preferably 1 most preferably 45 1, im.

Jampulver Jampulvret är foretradesvis ett jarnpulver innehallande minst 80 viktprocent metalliskt jam, foretradesvis minst 90 viktprocent metalliskt jam, mer foredraget minst 95 viktprocent metalliskt jam, mest foredraget minst 99 viktprocent metalliskt jam. Jampulvret kan vara ett jarnsvamppulver och/eller ett vattenatomiserat jampulver och/eller ett gasatomiserat jarnpulver och/eller eft jarnfilterstoft och/eller ett jarnslampulver. Exempelvis ar filterstoft X-RFS40 fran Hogands AB, Sverige ett lampligt pulver. 12 Jampulvret kan delvis eller fullstandigt ersattas av ett jamoxidpulver, exempelvis men inte begrdnsat till: pulver bestaende av ett eller flera fran gruppen FeO, Fe203, Fe304, Fe0(OH), (Fe203*H20). Jamoxidpulvret kan exempelvis vara frasspan. FOretrddesvis innehaller det jarnhaltiga pulvret minst 50 viktprocent metalliskt jam, mer foredraget minst 80 viktprocent metalliskt Fe, mest foredraget minst 90 viktprocent metalliskt Fe. Jam powder The jam powder is preferably an iron powder containing at least 80% by weight of metallic jam, preferably at least 90% by weight of metallic jam, more preferably at least 95% by weight of metallic jam, most preferably at least 99% by weight of metallic jam. The jam powder may be an iron mushroom powder and / or a water atomized jam powder and / or a gas atomized iron powder and / or after iron filter dust and / or an iron lamp powder. For example, filter dust X-RFS40 from Hogands AB, Sweden is a suitable powder. The jam powder may be partially or completely replaced by a jam oxide powder, for example but not limited to: powders consisting of one or more from the group FeO, Fe 2 O 3, Fe 3 O 4, FeO (OH), (Fe 2 O 3 * H 2 O). The jam oxide powder can be, for example, frasspan. Preferably, the iron-containing powder contains at least 50% by weight of metallic jam, more preferably at least 80% by weight of metallic Fe, most preferably at least 90% by weight of metallic Fe.

Foretrddesvis passerar minst 90 viktprocent, mer foredraget minst 99 viktprocent, av partiklama i det jamhaltiga pulvret genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 125 tm, mer ffiredraget 90 um. Mycket fint pulver ddr 10 minst 99 viktprocent passerar genom en 45 tm testsikt kan lampligen anvandas. Preferably, at least 90% by weight, more preferably at least 99% by weight, of the particles in the jam powder pass through a test screen in accordance with ISO 3310-1: 2000 with a nominal neck size of 125 .mu.m, more preferably 90 .mu.m. Very fine powder ddr 10 at least 99% by weight passes through a 45 tm test sieve can be suitably used.

Eventuellt kolpulver Rabriketterna innehaller foretradesvis en kolkdlla. I den foredragna utforingsformen är kolkdllan ett volframkarbidhaltigt pulver, dar kolhalten stakiometriskt motsvarar oxidhalten i rabriketterna. Emellertid kan aven ett kolpulver anvandas som antingen i kombination med ett volframkarbidhaltigt pulver eller som enda Kolpulvret är foretrddesvis valt fran gruppen av: subbituminosa kolsorter, bituminosa kolsorter, brunkol, antracit, koks, petroleumkoks och biokol sasom trakol, eller kolhaltiga pulver som bearbetats utifran dessa resurser. Kolpulvret kan exempelvis vara sot, kimrok, aktivt kol. Kolpulvret kan awn vara en blandning av olika kolpulver. FOr valet av kolpulver tas ffiretrddesvis hansyn till kolets reaktivitet. FOretrddesvis anvands kimrok. Tyskt brunkol (lignit), trdkol, bituminosa och subbituminosa kolsorter har ocksa jamforelsevis hog reaktivitet. Possibly charcoal powder The briquettes preferably contain a charcoal doll. In the preferred embodiment, the carbon particle is a tungsten carbide-containing powder, the carbon content of which stachiometrically corresponds to the oxide content of the briquettes. However, a carbon powder can also be used as either in combination with a tungsten carbide-containing powder or as the sole. The carbon powder is preferably selected from the group of: subbituminosa carbons, bituminosa carbons, lignite, anthracite, coke, petroleum coke and biochar such as carbonaceous carbon, resources. The carbon powder can be, for example, soot, carbon black, activated carbon. The carbon powder can awn be a mixture of different carbon powders. Before choosing carbon powder, consideration is given to the reactivity of the carbon. Preferably, kimrok is used. German lignite, charcoal, bituminosa and subbituminosa carbons also have comparatively high reactivity.

Foretrddesvis passerar minst 90 viktprocent, mer foredraget minst 99 viktprocent, av partiklama i kolpulvret genom en testsikt i enlighet med ISO 3310-1:2000 med nominell halstorlek av 125 gm, mer ffiredraget 45 um, mest foredraget 20 um. Kvantiteten av kolkallan (d.v.s. WC-pulver och/eller kolpulver) bestams foretrddesvis genom analys av kvantiteten reducerbara oxider i det volframhaltiga pulvret, jampulvret och det eventuella molybdenhaltiga pulvret. Foretrddesvis valjs kvantitetema av kolkdllan sa att de stokiometriskt motsvarar eller i nagon man overstiger kvantiteten reducerbara oxider i det volframhaltiga pulvret, jarnpulvret och det eventuella molybdenhaltiga pulvret. Emellertid kan kvantiteten av kolkallan awn vara understokiometrisk. Preferably at least 90% by weight, more preferably at least 99% by weight, of the particles in the carbon powder pass through a test screen in accordance with ISO 3310-1: 2000 with a nominal neck size of 125 μm, more preferably 45 μm, most preferably 20 μm. The quantity of the carbon dioxide (i.e. WC powder and / or carbon powder) is preferably determined by analyzing the quantity of reducible oxides in the tungsten-containing powder, the jam powder and the optional molybdenum-containing powder. Preferably, the quantities of the carbon dioxide are selected so that they stoichiometrically correspond to or in some cases exceed the quantity of reducible oxides in the tungsten-containing powder, the iron powder and the possible molybdenum-containing powder. However, the quantity of carbon awn may be understochiometric.

Kvantiteten av kolkallan kan optimeras genom att kolnivaerna och syrenivaerna i de reducerade briketterna mats — och genom att kvantiteten kolkdlla okas eller minskas for 13 att uppna onskade nivaer av kol och syre. Oxider som är svara att reducera med kol sasom Si, Ca, Al, och Mg kan tillatas upp till vissa nivaer beroende pa vilka tillampningar brikettema ska anvandas i. Exempelvis i manga tillampningar inom stalmetallurgi kan dessa oxider hanteras genom att de t.ex. avlagsnas i stalsmaltans slagg. Om mindre kvantiteter av dessa oxider och amnen onskas, kan renare kvaliteter av det volframhaltiga pulvret, jarnpulvret och det eventuella molybdenhaltiga pulvret anvandas, exempelvis kvaliteter som innehaller mindre eller inga kvantiteter av dessa oxider. The quantity of carbon dioxide can be optimized by feeding the carbon levels and oxygen levels in the reduced briquettes - and by increasing or decreasing the quantity of carbon dioxide to achieve desired levels of carbon and oxygen. Oxides which are suitable for reduction with carbon such as Si, Ca, Al, and Mg can be allowed up to certain levels depending on which applications the briquettes are to be used in. For example, in many applications in steel metallurgy these oxides can be handled by e.g. deposited in the steel malt slag. If smaller quantities of these oxides and substances are desired, purer grades of the tungsten-containing powder, the iron powder and any molybdenum-containing powder may be used, for example grades containing less or no quantities of these oxides.

Jam- och volframhaltiga rabriketter Rabrikettema utgors av den blandning som tillhandahalls i moment a). Vid beredning av blandningen är den totala mangden tillsatt vatten cirka 1-10 viktprocent av blandningen, mest foredraget 2-5 viktprocent. Rabrikettema kan torkas for att minska fukthalten till mindre an 5 viktprocent, eller mindre an 3 viktprocent. Jam- and tungsten-containing rabrikets The rabrikettes consist of the mixture provided in step a). When preparing the mixture, the total amount of added water is about 1-10% by weight of the mixture, most preferably 2-5% by weight. The briquettes can be dried to reduce the moisture content to less than 5% by weight, or less than 3% by weight.

Rabrikettema kan eventuellt innehalla upp till 10 viktprocent av ett eller flera organiska eller oorganiska bindemedel och/eller slaggbildare och/eller avsvavlingsmedel och/eller smOrjmedel. I en utforingsform är rabriketterna fria fran smOrjmedel, bindemedel, slaggbildare och avsvavlingsmedel. The briquettes may optionally contain up to 10% by weight of one or more organic or inorganic binders and / or slag formers and / or desulfurizing agents and / or lubricants. In one embodiment, the briquettes are free of lubricants, binders, slag formers and desulfurizing agents.

Rabrikettema är Overraskande starka och det kan dad& vara mojligt att anvanda de torkade rabrikettema for att direkt legera en stalsmalta med volfram, och eventuellt volfram och molybden, d.v.s. utan foregaende reduktion av rabrikettema. Rabrikettema kan vara ett kostnadseffektivt sat att legera med volfram, och eventuellt volfram och molybden. Rabriketterna kan aven delvis eller fullstandigt reduceras in genom att rabriketterna varms upp i eflerfoljande moment. The fabrics are surprisingly strong and it may be possible to use the dried fabrics to directly alloy a steel malt with tungsten, and possibly tungsten and molybdenum, i.e. without prior reduction of the branded theme. The briquettes can be a cost-effective way to alloy with tungsten, and possibly tungsten and molybdenum. The briquettes can also be partially or completely reduced by heating the briquettes in subsequent steps.

Jam- och volframhaltiga briketter Med den foreslagna processen kan det framstallas jam- och volframhaltiga briketter som bestar av, i viktprocent: 3-97, foretradesvis 30-95, Mo + W50-97, foretradesvis 70-95, 0< 10, foretradesvis < 5, mer foredraget < 3, < 10, foretradesvis < 5, mer foredraget < 1, Si< 10, foretradesvis < 5, mer foredraget < 1, Co< 10, foretradesvis < 5, mer foredraget < 1, Andra amnen < 5, foretradesvis < 1, 14 och resten Fe 2-40, foretradesvis 3-25, mer foredraget 5-20, mest foredraget 5-15. Jam- and tungsten-containing briquettes With the proposed process, jam- and tungsten-containing briquettes can be prepared which consist of, in weight percent: 3-97, preferably 30-95, Mo + W50-97, preferably 70-95, 0 <10, preferably < 5, more preferred <3, <10, preferably <5, more preferred <1, Si <10, preferably <5, more preferred <1, Co <10, preferably <5, more preferred <1, Second subject <5, preferably <1, 14 and the residue Fe 2-40, preferably 3-25, more preferably 5-20, most preferably 5-15.

Dessa briketter har en geometrisk densitet i intervallet 1-7 g/cm3, foretradesvis 2-6 g/cm3. 0, C kan inga. fran 0,05 % och hOgre. Si, Co kan ingâ fran sparmangder upp till de givna kvantiteterna. Foretradesvis tillsatts de inte avsiktligt men kan ingâ som fororeningar. Andra amnen utover W, Mo, Fe, 0, C, Si, Co kan inga fran sparmangder upp till de givna kvantiteterna. FOretradesvis tillsatts de inte avsiktligt men kan inga. som fororeningar. These briquettes have a geometric density in the range 1-7 g / cm 3, preferably 2-6 g / cm 3. 0, C can none. from 0.05% and higher. Si, Co can range from savings up to the given quantities. Preferably they are not added intentionally but may be included as contaminants. Other substances other than W, Mo, Fe, 0, C, Si, Co can not range from savings up to the given quantities. Preferably, they are not intentionally added but none can. as pollutants.

Enligt ett exempel bestar de jam- och volframhaltiga briketterna av, i viktprocent: 60-97, foretradesvis 80-95, 0< 10, foretradesvis < 5, mer foredraget < 3, < 10, foretradesvis < 5, mer foredraget < 1, Si< 10, foretradesvis < 5, mer foredraget < 1, Co< 10, foretradesvis < 5, mer foredraget < 1, Andra amnen < 5, foretradesvis < 1, och resten Fe 2-40, foretradesvis 3-25, mer foredraget 5-20, mest foredraget 5-15. According to one example, the jam and tungsten-containing briquettes consist of, in weight percent: 60-97, preferably 80-95, 0 <10, preferably <5, more preferably <3, <10, preferably <5, more preferably <1, Si <10, preferably <5, more preferably <1, Co <10, preferably <5, more preferably <1, Second subject <5, preferably <1, and the residue Fe 2-40, preferably 3-25, more preferably 5- 20, most lectured 5-15.

Dessa briketter har en geometrisk densitet i intervallet 2-8 g/cm3, foretradesvis 3-7 g/cm3. These briquettes have a geometric density in the range 2-8 g / cm 3, preferably 3-7 g / cm 3.

Dessa briketter kan ersatta konventionellt tillverkade jam-volfram-legeringar, niir de legeras med volfram vid smaltforfaranden. Briketterna kan framstallas till lagre kostnader an jarn-volfram av standardkvalitet. Dessutom loses briketterna pa grund av sina porosa strukturer upp snabbare an jam-volfram av standardkvalitet. These briquettes can replace conventionally made jam-tungsten alloys, as they are alloyed with tungsten in smelting processes. The briquettes can be manufactured at lower costs than standard quality iron-tungsten. In addition, due to their porous structures, the briquettes dissolve faster than standard-quality jam-tungsten.

Enligt ett annat exempel bestar de jam- och volframhaltiga brikettema av, i viktprocent: 20-80, foretradesvis 30-65, mer foredraget 40-55, Mo20-80, foretradesvis 30-65, mer foredraget 40-55, Mo + W> 50, foretradesvis > 70, 0< 10, foretradesvis < 5, mer foredraget < 3, < 10, foretradesvis < 5, mer foredraget < 1, Si< 10, foretradesvis < 5, mer foredraget < 1, Co< 10, foretradesvis < 5, mer foredraget < 1, Andra amnen < 5, foretradesvis < 1, och resten Fe 2-40, foretradesvis 3-25, mer foredraget 5-20, mest foredraget 5-15. According to another example, the jam and tungsten containing briquettes consist of, in weight percent: 20-80, preferably 30-65, more preferably 40-55, Mo 2 O-80, preferably 30-65, more preferably 40-55, Mo + W> 50, preferably> 70, 0 <10, preferably <5, more preferably <3, <10, preferably <5, more preferably <1, Si <10, preferably <5, more preferably <1, Co <10, preferably < 5, more preferably <1, Second subject <5, preferably <1, and the residue Fe 2-40, preferably 3-25, more preferably 5-20, most preferably 5-15.

Foretradesvis bestams viktforhallandet mellan molybden och volfram (Mo/W) till att vara inom intervallet 0,25-4, fOretradesvis 0,5-2, mer foredraget 0,8-1,25. Preferably, the weight ratio between molybdenum and tungsten (Mo / W) is determined to be in the range 0.25-4, preferably 0.5-2, more preferably 0.8-1.25.

Dessa briketter har en geometrisk densitet i intervallet 1-6 g/cm3, foretradesvis 2- g/cm3. These briquettes have a geometric density in the range 1-6 g / cm 3, preferably 2 g / cm 3.

Dessa jam-, volfram- och molybdenhaltiga briketter lampar sig for legering med volfram och molybden vid smaltforfaranden. De jam-, volfram- och molybdenhaltiga brikettema kan framstallas till jamforelsevis lagre kostnader. Dessutom loses brikettema pa grund av sina porosa strukturer upp snabbt i en stalsmalta. These jam-, tungsten- and molybdenum-containing briquettes are suitable for alloying with tungsten and molybdenum in smelting processes. The jam-, tungsten- and molybdenum-containing briquettes can be produced at comparatively lower costs. In addition, due to their porous structures, the briquettes dissolve quickly in a steel malt.

Kvantiteten av andra amnen regleras huvudsakligen av renheten hos det volframhaltiga pulvret och det eventuella molybdenhaltiga pulvret. Renheten hos det jarnhaltiga pulvret och det eventuella kolpulvret kan givetvis paverka kvantiteten av andra amnen. The quantity of other substances is mainly controlled by the purity of the tungsten-containing powder and any molybdenum-containing powder. The purity of the ferrous powder and any carbon powder can of course affect the quantity of other substances.

Kvavehalten beror huvudsakligen pa kvavenivaema i atmosfaren under uppvarmning, reduktion och kylning av brikettema. Genom att atmosfaren i dessa moment regleras kan kvavehalten goras lagre an 0,5 viktprocent, foretradesvis lagre an 0,1 viktprocent och mest foredraget lagre an 0,05 viktprocent. The nitrogen content depends mainly on the nitrogen levels in the atmosphere during heating, reduction and cooling of the briquettes. By regulating the atmosphere in these moments, the nitrogen content can be made lower by 0.5% by weight, preferably lower by 0.1% by weight and most preferably lower by 0.05% by weight.

Claims (9)

1. a) A process for producing iron and tungsten containing briquettes the processincluding the steps of: providing a niixture con1prising (in weight-%): 2-97 tungsten oxides tungsten containing powder containing at least one of and tungsten carbides. optionally 0. 1-25 carbon powder, 2-90 nio lybdenuni containing powder,balance 1-40 iron powder b) adding to the niixture: C) water,optionally one or n1ore of: slag forrner, desulfurizer, briquetting to provide a plurality of green briquettes. 2. A process according to claini 1 wherein the niixture fulf1lling the condition: > 50 n1olybdenun1 containing powder + tungsten containing powder. 3. A process according to claini l and 2 wherein the process further includes drying the green briquettes at a temperature less than 200 °C, preferably less than 150 °C, until the n1oisture content is less than 10 % by weight of the briquettes, preferably less than 5 % by weight. 4. A process according to any one of claims 1- 3 wherein the process furtherincludes reducing the green briquettes at a temperature in the range of 1050-1300 °C, preferably 1100-1300 °C, most preferably 1150-1250 °C. 5. A process according to claim 4, wherein the method includes one or more of thefollowing steps:d) cooling the reduced briquettes in a non-oxidising atmosphere to atemperature below 200 °C , more preferably below 150 °C, preferably in an inert atmosphere; 6. Iron and tungsten containing green briquettes having a dry matter composition inweight-% of:a) 90-100 of a mixture comprising in weight % of the mixture:2-97 tungsten containing powder containing at least one of tungsten oxides and tungsten carbides, optionally 0. 1-25 carbon powder, 2-90 mo lybdenum containing powderbalance
1. -40 iron powder; b) optionally up to 10 of a slag former and/or a desulfurizer. 7. Iron and tungsten containing briquettes consisting of in weight %: W 20-80Mo 20-80Mo+ W 50-97O S 10C S 10Si S 10Co S 10 Other elements S 5 and balance Fe
2. -40. 8. Iron and tungsten briquettes according to claim 7 consisting of in Weight %: O S 5, more preferably S 3,C S 5, more preferably S 1,Si S 5, more preferably S 1,Co S 5, more preferably S 1, Other elements S 5, preferably S 1, and balance Fe 2-40, preferably
3. -25, more preferably 5-20, most preferably 5-15. 9. Iron and tungsten containing briquettes according to claim 7 consisting of in Weight %: W 30-65, preferably 40-55, Mo 30-65, preferably 40-55, Mo + W >70, O S 10, preferably S 5, more preferably S 3,C S10, preferably S 5, more preferably S 1,Si S 10, preferably S 5, more preferably S 1,Co S 10, preferably S 5, more preferably S 1, Other elements S 5, preferably S 1, and balance Fe 2-40, preferably 3-25, more preferably 5-20, most preferably 5-15.
SE1300384A 2013-05-27 2013-05-27 Iron and tungsten-containing briquettes SE537464C2 (en)

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AT342099B (en) * 1975-09-22 1978-03-10 Treibacher Chemische Werke Ag ADDITIVES FOR STEEL MELTING AND PROCESS FOR MANUFACTURING SUCH ADDITIVES
US4113479A (en) * 1976-02-27 1978-09-12 Amax Inc. Vacuum smelting process for producing ferrotungsten
CA1097950A (en) * 1977-02-14 1981-03-24 Donald O. Buker Vacuum smelting process for producing ferrotungsten
AT409271B (en) * 2000-02-04 2002-07-25 Treibacher Ind Ag METHOD FOR PRODUCING AGGLOMERATES, CONTAINING IRON AND AT LEAST ONE OTHER ELEMENT OF GROUPS 5 OR 6 OF THE PERIODIC SYSTEM
BR112012009805A2 (en) * 2009-10-26 2016-11-22 Minpro Aktiebolag tungsten carbide recycling
EP2597165B1 (en) * 2011-11-25 2014-09-03 AB Ferrolegeringar Iron and molybdenum containing pellets
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