EP3003606A1 - Eisen- und wolframhaltige briketts - Google Patents
Eisen- und wolframhaltige brikettsInfo
- Publication number
- EP3003606A1 EP3003606A1 EP14805161.8A EP14805161A EP3003606A1 EP 3003606 A1 EP3003606 A1 EP 3003606A1 EP 14805161 A EP14805161 A EP 14805161A EP 3003606 A1 EP3003606 A1 EP 3003606A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tungsten
- weight
- powder
- briquettes
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 78
- 239000010937 tungsten Substances 0.000 title claims abstract description 76
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 128
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052750 molybdenum Inorganic materials 0.000 claims description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 27
- 239000011733 molybdenum Substances 0.000 claims description 27
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- -1 tungsten carbides Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004484 Briquette Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 description 31
- 239000007789 gas Substances 0.000 description 25
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 25
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000161 steel melt Substances 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910001021 Ferroalloy Inorganic materials 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- AHIVCQLQCIBVOS-UHFFFAOYSA-N [Fe].[W] Chemical compound [Fe].[W] AHIVCQLQCIBVOS-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009865 steel metallurgy Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/001—Starting from powder comprising reducible metal compounds
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0235—Starting from compounds, e.g. oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
Definitions
- the present invention relates to a process for producing iron and tungsten containing briquettes.
- the invention also relates to briquettes produced by the process.
- WO 11053231 discloses a method for producing an iron- and tungsten containing powder or powder agglomerate.
- a tungsten carbide containing powder is mixed with an iron oxide powder and/or a tungsten oxide containing powder and optionally an iron powder.
- the mix is heated in a neutral or weakly reduced atmosphere.
- WO2008091210 discloses an iron a tungsten containing powder comprising 30-60 % by weight of W and balance Iron.
- the powder is made by mixing an iron powder with a W0 3 -powder.
- a bullet can be produced from the powder.
- It is an object of the invention provide a novel iron and tungsten containing material suitable for tungsten addition in melting industries e.g. steel, foundry and superalloy industry, and a process for producing such material in a comparably cost efficient manner.
- At least one of the above mentioned objects is at least to some extent achieved by a process for producing an iron and tungsten containing briquettes including the steps of: a) providing a mixture comprising (in weight-%):
- a liquid preferably water
- the non-reduced green briquettes may be used as a substitute for traditionally manufactured ferrotungsten and/or ferromolybdenum alloys, when alloying the melt in industrial production.
- the green briquettes can be produced at lower costs than standard grades of ferroalloys.
- Their porous structure facilitates quick dissolving time in a steel melt.
- the briquettes can be easily transported on a conveying belt without the risk of rolling off.
- the total amount of added water is around 1-10 % by weight the mixture, more preferably 2-5 % by weight.
- neither binder nor slag former is used.
- the iron containing powder when mixed in wet condition strengthens the briquettes, making the use of a binder unnecessary. Thereby the amount of impurities can be reduced.
- the method includes the step:
- the optional drying step includes at least one of the following:
- drying the green briquettes to a moisture content less than 5 % by weight, preferably less than 3 % by weight; drying the green briquettes at a temperature in the range of 50-250 °C, preferably 80-200 °C, more preferably 100-150 °C.
- the briquettes may also be dried without active heating, e.g. in ambient air temperature. In a dryer vapour may be removed by a gas steam or by vacuum. For improved process economy, drying time in a dryer is preferably in the range of 10- 120 minutes, more preferably 20-60 minutes. But longer drying times are of course viable.
- the moisture content is defined as water present in the green briquettes apart from water of crystallization.
- the moisture content can be determined by a LOD (loss on drying) analysis in accordance to ASTM D2216 - 10.
- Dry matter composition refers to the composition for a dried specimen, i.e. excluding any moisture present in the green briquettes.
- the method includes the step:
- the reduction step includes at least one of the following:
- the reduction time can be optimised by measuring the formation of CO and C0 2 ; in particular CO since C0 2 is mainly formed during the first minutes of reduction where after CO formation is dominating until the carbon source is consumed or all reducible oxides have been reduced.
- the reduction time is at most 10 hours, preferably at most 2 hours, more preferably at most 1 hour.
- the reduction temperature, and the relation between carbon and reducible oxides in the briquettes; the reducible oxides of the briquettes can be partially or fully reduced.
- the atmosphere within the furnace is preferably controlled by supplying an inert or a reducing gas, preferably a weakly reducing gas, at one end of the furnace and evacuating gases (e.g. reaction gases (e.g. CO, C0 2, and H 2 0) and the supplied gas) at the opposite end, more preferably, supplying the inert or reducing gas counter current at an outlet side of the furnace, and evacuating gases at an inlet side of the furnace.
- the inert or reducing gas is preferably supplied counter flow.
- the inert or a reducing gas may e.g. be argon, N 2; H 2 , or any mixture of H 2 /N 2 (e.g. 5:95 by vol.).
- the reduction furnace is preferably a continuous furnace but may also be a batch furnace.
- a continuous furnace the briquettes are conveyed from an inlet to and outlet during the reduction.
- furnaces are for example rotary kilns, rotary heart furnaces, shaft furnaces, grate kilns, travelling grate kilns, tunnel furnaces or batch furnaces.
- Other kinds of furnaces used in solid state direct reduction of metal oxides may also be employed.
- a belt furnace is used.
- the reduction furnace operates at 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 1.05-1.2 atm.
- the atmosphere within the reduction furnace is preferably controlled by supplying an inert or a reducing gas, preferably a weakly reducing gas, at one end of the furnace and evacuating gases (e.g. reaction gases (e.g. CO, C0 2; and H 2 0) and the supplied gas) at the opposite end, more preferably, supplying the inert or reducing gas counter current at the outlet side of the furnace, and evacuating gases at the inlet side of the furnace.
- the inert or reducing gas is preferably supplied counter flow.
- the gas supplied may include argon, N 2; H 2; CO, C02 or any mixture of them.
- the atmosphere comprises 20-60 vol % of H 2 and balance N 2 .
- Such atmosphere may reduce N 2 uptake, compared to e.g. H 2 /N 2 (5:95), and it may increase the density of the reduced pellets.
- the atmosphere may also be supplied with CO, e.g. from burning natural gas. Of course, other gas mixes being inert or reducing may be supplied to the furnace.
- the method further includes the step:
- a non-oxidising atmosphere e.g. reducing or inert
- the atmosphere during cooling may e.g. be argon, N 2; H 2 , or any mixture of H 2 /N 2 (e.g 5:95 by vol.). Other atmospheres may also be employed. If it is desirable to have very low levels of nitrogen in the briquettes, the briquettes may be cooled in a nitrogen free atmosphere such as for example an argon gas atmosphere.
- briquetting is performed at a briquetting pressure in the range of 80- 1000 kg/cm2, preferably 100-500 kg/cm2.
- briquetting is performed at a briquetting pressure in the range of 1000-10000 kg/cm2, preferably 2000-5000 kg/cm2.
- the briquetting machine is a roller press. However, other kinds of briquetting machines may be used.
- the green briquettes are heat treated at a lower temperature before reduction. Preferably heat treating the green briquettes at a temperature in the range of 200-800 °C, more preferably 400-700 °C. Preferably, the optional heat treating at lower temperature is performed from 10 minutes to less than 2 hours, preferably less than 1 hour. By heat- treating at lower temperatures the optional lubricant (if present) can be burned off in a controlled manner. In addition molybdenum trioxide (if present) may be reduced to molybdenum dioxide.
- the optional heat treating at 200-800 °C can be performed in the same furnace as the reduction.
- the optional heat treating and optional drying may also be combined.
- lubricants and/or binders and/or slag formers and/or desulfurizer can be added when mixing.
- the optional binders may be organic or inorganic binders.
- the binders may e.g. be a carbon containing binders partially replacing the carbonaceous powder.
- Other binders may e.g. be bentonite and/or dextrin and/or sodium silicate and/or lime and/or gelatin.
- the optional slag former may be limestone, dolomite, and/or olivine.
- the total amount of lubricants and/or binders and/or slag formers and/or desulfurizers can be 0.1-10 % by weight of the dry matter content of the green briquette, more preferably less than 5 wt%. It may be in the range of 1-10 % by weight.
- the binders are optional since the green briquettes by the water and iron addition becomes sufficiently strong to be reduced in the reduction furnace without severely cracking. If added the lubricant is preferably added in amounts of 0.1-2 % of the the dry matter content of the briquette, e.g. about 0.5-1 % by weight.
- the lubricant can e.g. be zinc stearate. However, other lubricants that are used in powder metallurgy may be added.
- the mixture the briquettes may contain further elements including oxides that are difficult to reduce.
- the amount of such elements are mainly determined by the purity of the tungsten containing powder and the optional molybdenum containing powder, but may also come from impurities in the iron powder, the carbon powder, and from reactions with elements in the surrounding atmosphere during heating, reduction, or cooling.
- the total process is endothermic and requires heat.
- oxygen gas or air can be provided in a pre-heating zone to react with the formed carbon monoxide to form carbon dioxide gas. If air is used the nitrogen uptake of the briquettes may increase. Using oxygen the nitrogen uptake during the heating and the reduction step can be minimised.
- the furnace 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 include a pre-reduction zone, downstream the drying zone if such is used, and operating in the range of 200-800 °C, preferably 400-700 °C.
- the iron and tungsten containing green briquettes having a dry matter composition in weight-% of:
- ⁇ 10 lubricant and/or binder and/or slag former and/or a desulfurizer Preferably the reduced iron and tungsten containing briquettes consisting of in weight
- the briquettes can substitute for traditionally manufactured ferroalloys, when alloying with tungsten and optionally tungsten/molybdenum in melting practices.
- the briquettes can be produced at lower costs than standard grades of ferrotungsten.
- the briquettes dissolve quicker than standard grades of ferrotungsten.
- the relative amount of carbon in relation to the amount of reducible oxides, and the reduction temperature - the oxygen content in the briquettes can be partially or fully reduced.
- the briquettes can be easily transported on a conveying belt without the risk of rolling off.
- the mixture provided in step a) comprises (in weight-%):
- iron containing powder 1-40 iron containing powder.
- the iron powder is 2-25 % by weight, more preferably 3-15 % by weight.
- the tungsten containing powder is at least 20 % by weight.
- the tungsten containing powder + molybdenum containing powder is more than 50 % by weight of the mixture, more preferably more than 70 % by weight of the mixture.
- the mixture consists of (in weight-%):
- the tungsten containing powder includes tungsten oxides and tungsten carbides.
- the reducible oxides in the tungsten containing powder and the iron containing powder are stoichiometric matched with carbon of the tungsten carbides, so that after a reduction the carbon content 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 % by weight, and oxygen is less than 10 % by weight, preferably less than 5 % by weight, most preferably less than 3 % by weight.
- iron and tungsten containing briquettes can be produced that essentially consists of iron and tungsten and unavoidable impurities.
- Iron and tungsten containing briquettes that consist of iron and tungsten and
- unavoidable impurities can also be produced from a mixture where tungsten carbides is partially or fully replaced by a carbon powder, i.e. so that carbon of tungsten carbides and/or carbon powder stoichiometric matches the reducible oxides in tungsten containing powder and the iron powder.
- Iron and tungsten containing briquettes that consists of iron, tungsten and molybdenum and unavoidable impurities can be produced from the mixture by adding the optional molybdenum containing powder.
- carbon from the tungsten carbides and/or carbon powder is stoichiometric matched with the reducible oxides in molybdenum containing powder, the tungsten containing powder and the iron powder.
- the tungsten containing powder preferably 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 W0 3 , preferably at least 95 % by weight of WO 3 , or a mixture of these powders.
- the carbon and oxygen is balanced so that after reduction, the carbon content 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 % by weight, and oxygen is less than 10 % by weight, preferably less than 5 % by weight, most preferably less than 3 % by weight.
- the relative amounts of molybdenum and tungsten can be varied by changing the relative amounts of the tungsten containing powder and molybdenum containing powder, while considering the carbon and oxygen balance.
- the weight ratio between tungsten carbide and tungsten oxide is within the range of 0.5-5, preferably 1-4, more preferably 1.5-3.
- An optimal balance is about 2. Thereby the tungsten carbide can match the tungsten oxide without the need of carbon powder addition.
- the weight ratio between molybdenum and tungsten are determined to be within the range 0.25 - 4, preferably 0.5 - 2, more preferably 0.8-1.25.
- the tungsten containing powder is preferably one of:
- The_tungsten carbide containing powder is a powder that comprises tungsten carbides contained in a metal matrix.
- the tungsten carbide containing powder is obtained from tungsten cemented carbide scrap.
- the tungsten carbide containing powder preferably comprises 1-10 % by weight of carbon, balance tungsten and incidental impurities.
- the tungsten carbide containing powder may also include alloy elements which have formed a matrix (binding material) for the cemented tungsten carbide material.
- the proportion of carbide phase is generally between 70-97% of the total weight of the composite.
- the carbon is present in the powder particles in the form of tungsten carbide grains, and typically the grain size averages between 0.10 ⁇ and 15 ⁇ .
- Any powder particle may include several tungsten carbide grains, in particular if the particle sizes are large. Further, the tungsten carbide containing powder may include powder particles that are void of any tungsten carbide grains; however most of the powder particles will include one or more grains of tungsten carbide.
- Some tungsten carbide powder can contain cobalt up to 15 %.by weight; typically around 1-10 % by weight of Co.
- the tool material in circuit board drills typically comprises fine grained, cemented tungsten carbides existing in a cobalt matrix, the amount of which represents 6 percent of the total weight of the tool material, while coarse grain tungsten carbide materials typically are used for the tool material of mine drills, where the cobalt content of the cemented carbide material is about 10 weight-%.
- These powders can be used if cobalt can be allowed or is desirable in the briquette to be produced. If not, these powders can be used after being leached from cobalt.
- tungsten carbide containing powders from scrap that comprises 1-10 % by weight Co, usually in amounts of 3-8 % by weight Co, can be hydrometallurgical leached to reduce the cobalt content to be less than 1 % by weight Co, preferably less than 0.5 % by weight Co, more preferably less than 0.2 % by weight Co.
- the cobalt from the leaching process can be recycled and employed as a
- tungsten carbide powder that already is low or void of cobalt can be used. I.e. a powder that contains less than 1 % by weight Co, more preferably less than 0.5 % by weight Co, even more preferably less than 0.2 % by weight Co.
- the tungsten carbide powder contains at least 90 % by weight of WC, more preferably at least 95 % by weight.
- Very fine powder where at least 99 % by weight, passes through a test sieve of 45 ⁇ can suitably be used.
- the tungsten oxide containing powder may be an iron and tungsten oxide containing powder, more preferably iron tungstate in the form of the mineral Ferberite.
- a feberite that contains over 60 % of W0 3 , more preferably at least 70 % WO 3 .
- the ferberite is crushed and/or milled and/or ground to a powder so that at least 80 % by weight of the particles, preferably at least 90 %, passes through a test sieve in accordance to ISO 3310-1 :2000 having nominal aperture sizes of 250 ⁇ , more preferably 125 ⁇ .
- the tungsten oxide containing powder may also be a pure tungsten oxide powder containing less than 5 % by weight of other elements besides W and O, preferably less than 1 % by weight of other elements.
- At least 80 % by weight of the particles, more preferably at least 90 % by weight of the particles of the tungsten oxide powder pass through a test sieve in accordance to ISO 3310-1 :2000 having nominal aperture sizes of 250 ⁇ , more preferably 125 ⁇ . most preferably 90 ⁇ .
- Very fine powder where at least 99 % by weight, passes through a test sieve of 45 ⁇ can suitably be used.
- the tungsten oxide containing powder may also be a mix of iron tungstate and pure tungsten oxide powder.
- the molybdenum containing powder is preferably a molybdenum oxide powder.
- the powder preferably consists of molybdenum dioxide and/or molybdenum trioxide powder.
- the molybdenum oxide powder should contain 50-80 % by weight of Mo, the remaining elements being oxygen and impurities.
- the impurities are less than 10 % by weight, more preferably less than 5 % by weight, most preferably less than 1% by weight.
- At least 90 % by weight, more preferably at least 99 % by weight, of the particles of the molybdenum oxide powder pass through a test sieve in accordance to ISO 3310-1 :2000 having nominal aperture sizes of 250 ⁇ , more preferably 125 ⁇ , most preferably 45 ⁇ .
- the iron containing powder is preferably an iron powder containing at least 80 wt% metallic iron, preferably at least 90 wt% metallic iron, more preferably at least 95 wt% metallic iron, most preferably at least 99 wt% metallic iron.
- the iron powder can be an iron sponge powder and/or a water atomised iron powder and/or a gas atomised iron powder and/or an iron filter dust and/or an iron sludge powder.
- filter dust X-RFS40 from Hoganas AB, Sweden is a suitable powder.
- the iron powder may partly or fully be replaced by an iron oxide powder, for instance but not limited to: powder consisting of one or more from the group of FeO, Fe 2 0 3 , Fe 3 0 4 , FeO(OH), (Fe 2 O 3 *H 2 0).
- the iron oxide powder may e.g. be mill scale.
- the iron containing powder contains at least 50 % be weight of metallic iron, more preferably at least 80 wt% metallic Fe, most preferably at least 90 wt% metallic Fe.
- the iron containing powder may also be a ferberite, FeW04. It may also be a mix between one or more powders of FeO, Fe 2 0 3 , Fe 3 0 4 , FeO(OH), (Fe 2 O 3 *H 2 0),
- At least 90 % by weight, more preferably at least 99 % by weight, of the particles of the iron containing powder pass through a test sieve in accordance to ISO 3310-1 :2000 having nominal aperture sizes of 125 ⁇ , more preferably 90 ⁇ .
- Very fine powder where at least 99 % by weight, passes through a test sieve of 45 ⁇ can suitably be used.
- the green briquettes preferably includes a carbon source.
- the carbon source is a tungsten carbide containing powder, where the carbon content stoichiometric matches the oxide contents in the green briquettes.
- a carbon powder may also be used as the carbon source, either in combination with a tungsten carbide containing powder or as the sole carbon source.
- the carbon powder is preferably chosen from the group of: sub-bituminous coals, bituminous coals, lignite, anthracite, graphite, coke, petroleum coke, and bio-carbons such as charcoal, or carbon containing powders processed from these resources.
- the carbon powder may e.g. be soot, carbon black, activated carbon.
- the carbon powder can also be a mixture of different carbon powders.
- the reactivity of the carbon is preferably taken into consideration.
- carbon black is used.
- German brown coal (lignite), charcoal, bituminous and sub-bituminous coals also have comparably high reactivity.
- Graphite is also suitable.
- at least 90 % by weight, more preferably at least 99 % by weight, of the particles of the carbon powder pass through a test sieve in accordance to ISO 3310- 1 :2000 having nominal aperture sizes of 125 ⁇ , more preferably 45 ⁇ , most preferably 20 ⁇ .
- the amount of the carbon source (i.e. WC-powder and/or carbon powder) is preferably determined by analysing the amount of reducible oxides in the tungsten containing powder, the iron powder, and the optional molybdenum containing powder.
- the amounts of the carbon source is chosen to stoichiometric match or slightly exceed the amount of reducible oxides in the tungsten containing powder, the iron powder, and the optional molybdenum containing powder.
- the amount of the carbon source may also be sub-stoichiometric.
- the amount of the carbon source can be optimised by measuring the carbon levels and the oxygen levels in the reduced briquettes - increasing or decreasing the amount of carbon source to achieve desired levels of carbon and oxygen.
- Oxides which are difficult to reduce with carbon such as Si, Ca, Al, and Mg may be allowed up to certain levels depending on in which applications the briquettes are to be used in. For instance in many applications of steel metallurgy these oxides can be handled e.g. by removing them in the slag of steel melt. If lower amounts of these oxides and elements are desired, purer grades of the tungsten containing powder, the iron powder, and the optional molybdenum containing powder can be used, e.g. grades that contains less or no amounts of these oxides.
- the green briquettes comprises of the mixture provided in step a).
- the total amount of added water is around 1-10 % by weight of the mixture, more preferably 2-5 % by weight.
- the green briquettes may be dried to reduce the moisture content to less than 5 % by weight, or less than 3 % by weight.
- the green briquettes may optionally comprise up to 10 % by weight of one or more organic or inorganic binders and/or slag formers and/or desulfurizers and/ or lubricants.
- the green briquettes are void of lubricants, binders, slag formers and desulfurizers.
- the green briquettes are surprisingly strong and it may therefore be possible to use the dried green briquettes to directly alloy a steel melt with tungsten and optionally tungsten and molybdenum, i.e. without prior reduction of the green briquettes.
- the green briquettes can be cost efficient way of alloying with tungsten and optionally tungsten and molybdenum.
- the green briquettes may also be partially or fully reduced in by heating the green briquettes in subsequent steps.
- Iron and tungsten containing briquettes can be produced by the suggested process that consists of in weight %:
- Fe 2-40 preferably 3-25, more preferably 5-20, most preferably 5-15.
- These briquettes have a geometric density in the range of 2-6 g/cm 3 , preferably 4-5.5 g/cm 3 .
- O, C may be present from 0.05 % and higher.
- Si, Co may be present from traces up to the given amounts. They are preferably not deliberately added but may be present as impurities.
- Other elements apart from W, Mo, Fe, O, C, Si, Co may be present from traces up to the given amounts. They are preferably not deliberately added but may be present as impurities.
- the iron and tungsten containing briquettes consists of in weight %:
- Fe 2-40 preferably 3-25, more preferably 5-20, most preferably 5-15.
- These briquettes have a geometric density in the range of 2-8 g/cm 3 , preferably 3-7 g/cm 3 , more preferably 4-6 g/cm 3 .
- the geometric density may be in the range of 4.5-5.5 g/cm 3 .
- briquettes may substitute traditionally manufactured ferrotungsten alloys, when alloying with tungsten in melting practices.
- the briquettes can be produced at lower costs than standard grades of ferrotungsten. Furthermore, due to their porous structures the briquettes dissolves quicker than standard grades of ferrotungsten.
- the iron and tungsten containing briquettes consists of in weight %:
- W 20-80 preferably 30-65, more preferably 40-55,
- Mo 20-80 preferably 30-65, more preferably 40-55,
- Mo + W > 50, preferably >70
- the weight ratio of molybdenum and tungsten are determined to be within the range 0.25 - 4, preferably 0.5 - 2, more preferably 0.8-1.25.
- These briquettes have a geometric density in the range of 1-6 g/cm 3 , preferably 2-5 g/cm 3 .
- These iron, tungsten and molybdenum containing briquettes are suitable for alloying with tungsten and molybdenum in melting practices.
- molybdenum containing briquettes can be produced at comparably lower costs.
- the briquettes dissolves quickly in a steel melt.
- the amount of other elements is mainly controlled by the purity of the tungsten containing powder and the optional molybdenum containing powder.
- the purity of the iron containing powder and optional carbon powder may of course influence the amount of other elements.
- the nitrogen content mainly depends on the nitrogen levels in the atmosphere during heating, reduction and cooling of the briquettes. By controlling the atmosphere in these steps the nitrogen content can be made lower than 0.5 wt%, preferably lower than 0.1 wt% and most preferably lower than 0.05 wt%.
- the green pellets were reduced in a batch furnace at a temperature of 1200 °C for a time period of 2 hours, in a 95 vol-% N 2 and 5 vol-% H 2 atmosphere.
- the briquettes were thereafter allowed to cool to a temperature around 100 °C before evacuating the atmosphere and removal from the furnace.
- the average geometric density of the reduced briquettes was determined to be 5.9 g/cm 3 as measured according to ASTM
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE1300384A SE537464C2 (sv) | 2013-05-27 | 2013-05-27 | Järn- och volframhaltiga briketter |
PCT/SE2014/050654 WO2014193299A1 (en) | 2013-05-27 | 2014-05-27 | Iron and tungsten containing briquettes |
Publications (2)
Publication Number | Publication Date |
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EP3003606A1 true EP3003606A1 (de) | 2016-04-13 |
EP3003606A4 EP3003606A4 (de) | 2017-02-15 |
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Application Number | Title | Priority Date | Filing Date |
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EP14805161.8A Withdrawn EP3003606A4 (de) | 2013-05-27 | 2014-05-27 | Eisen- und wolframhaltige briketts |
Country Status (4)
Country | Link |
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EP (1) | EP3003606A4 (de) |
SE (1) | SE537464C2 (de) |
TW (1) | TW201501839A (de) |
WO (1) | WO2014193299A1 (de) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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AT342099B (de) * | 1975-09-22 | 1978-03-10 | Treibacher Chemische Werke Ag | Zusatzmittel fur stahlschmelzen und verfahren zur herstellung solcher zusatzmittel |
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 (de) * | 2000-02-04 | 2002-07-25 | Treibacher Ind Ag | Verfahren zur herstellung von agglomeraten, enthaltend eisen und mindestens ein weiteres element der gruppen 5 oder 6 des periodensystems |
EP2427286A4 (de) * | 2009-10-26 | 2012-06-27 | Minpro Aktiebolag | Recycling von wolframcarbiden |
EP2597165B1 (de) * | 2011-11-25 | 2014-09-03 | AB Ferrolegeringar | Eisen- und molybdänhaltige Pellets |
TW201430143A (zh) * | 2012-09-05 | 2014-08-01 | Ferrolegeringar Ab | 含有鐵及鎢之丸粒 |
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2013
- 2013-05-27 SE SE1300384A patent/SE537464C2/sv not_active IP Right Cessation
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2014
- 2014-05-27 EP EP14805161.8A patent/EP3003606A4/de not_active Withdrawn
- 2014-05-27 TW TW103118375A patent/TW201501839A/zh unknown
- 2014-05-27 WO PCT/SE2014/050654 patent/WO2014193299A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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WO2014193299A1 (en) | 2014-12-04 |
TW201501839A (zh) | 2015-01-16 |
SE1300384A1 (sv) | 2014-11-28 |
SE537464C2 (sv) | 2015-05-12 |
EP3003606A4 (de) | 2017-02-15 |
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