EP3628753A1 - Verfahren zur herstellung von eisen- und chromhaltigen pellets - Google Patents
Verfahren zur herstellung von eisen- und chromhaltigen pellets Download PDFInfo
- Publication number
- EP3628753A1 EP3628753A1 EP18196811.6A EP18196811A EP3628753A1 EP 3628753 A1 EP3628753 A1 EP 3628753A1 EP 18196811 A EP18196811 A EP 18196811A EP 3628753 A1 EP3628753 A1 EP 3628753A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- chrome
- iron
- pellets
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000008188 pellet Substances 0.000 title claims abstract description 118
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000010909 process residue Substances 0.000 claims abstract description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003830 anthracite Substances 0.000 claims abstract description 6
- 239000000571 coke Substances 0.000 claims abstract description 5
- 239000002802 bituminous coal Substances 0.000 claims abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005453 pelletization Methods 0.000 description 9
- 239000000440 bentonite Substances 0.000 description 7
- 229910000278 bentonite Inorganic materials 0.000 description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- 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
Definitions
- the invention relates to a process for preparing iron- and chrome-containing pellets, to iron- and chrome-containing pellets and their use for the preparation of Ferrochrome as well as to a process for the preparation of Ferrochrome using the iron- and chrome-containing pellets.
- Ferrochrome A widely used iron- and chrome-containing alloy is the so called Ferrochrome.
- Ferrochrome is used in the stainless-steel industry to increase the resistivity of steel against water and air to prevent the formation of rust.
- the iron and chrome source for the Ferrochrome production is usually chromite, a chrome ore, which is found in some parts of the world, like in South Africa.
- the production of Ferrochrome is carried out in huge electrically heated arc furnaces or blast furnaces at high temperatures, using a carbon based reductant which can be part of the electrode or which is mixed in the chrome ore, or both.
- the consumption of electricity is significant and determines the cost effectiveness of a process using electrically heated furnaces.
- the process results in a liquid, molten alloy which is casted in casts, and a layer of partially molten residue floating on top of the liquid metal, the slag.
- the pellets produced according to the process of ZA2004-03429A and according to Minerals Engineering (2012), 34, 55-62 are made of chrome ore, a carbonaceous reductant and a so-called unconverted or non-activated binding agent.
- the binding agent is a mainly silica based clay, like Bentonite. Bentonite comprises ca. 24 weight-% of silicon.
- the binding agent Bentonite contains neither iron nor chrome and thus, cannot contribute to the formation of Ferrochrome afterwards. Instead, the silica contained in Bentonite increases the amount of useless and costly slag. Slag is not only an undesired by-product in the process for the production of Ferrochrome but furthermore its formation requires additional electrical energy (e.g. for heating and for the reduced throughput of the furnace).
- Another disadvantage of the process is the effect of Bentonite on the density of the wet pellets fed into a tunnel furnace for pre-calcining step.
- the Bentonite is absorbing water and decreases the density of the pellets, which leads to a lower throughput of material through the tunnel furnace, as this is limited by volume per time unit, but the producer get paid by mass of pellets produced.
- the pore volume of the pellets is important, as the reducing gases formed in the arc furnace process need to reach the oxides in the pellets. So, a higher Chrome content and an increased density of the raw, dried pellets is desired with only small changes in the porosity of the indurated, calcined pellets. This results in lower slag production, higher throughput through the (tunnel-) furnace.
- the pellets should preferably be usable in a process for the preparation of Ferrochrome that is more energy-efficient.
- the pellets should be prepared essentially without using carbonaceous reductants and/or reducing components, which reduce the metal oxide of the pellets during calcination.
- COPR fulfills all of the above requirements at the same or higher level than the binder used as state-of-the-art.
- the invention therefore provides a process for preparing iron- and chrome-containing pellets comprising the steps:
- the chrome ore material used in step a) contains:
- the worldwide largest chrome ores deposits are located in South Africa, countries, Turkey and the Philippines and in some other countries.
- the chrome ore is divided in two categories: The metallurgical grade with ⁇ 45 weight-% of Cr 2 O 3 and the chemical grade with ⁇ 45% weight-% and ⁇ 40 weight-% of Cr 2 O 3 .
- the largest known deposit of chrome ore is found in clouds with over 300 million tons.
- Chrome Ore Process Residue sometimes also named chromite ore processing residue is known to person skilled in the art as a waste stream comprising chrome and other metal oxides from the industrial production of chromate.
- the Chrome Ore Process Residue (COPR) used in step a) is preferably a by-product from the sodium monochromate production process. Therein, chrome ore is mixed with soda ash and heated to a temperature of about 1200°C under oxidizing condition. The reaction mixture is leached with water, and the dried solid residue is the so-called Chrome Ore Process Residue (COPR).
- the COPR is obtained in the process for producing sodium monochromate from chromite via an oxidative alkaline digestion with sodium carbonate (no lime process, CaO content of ⁇ 5% by weight).
- COPR contains metal oxides such as chromium(III) oxide (Cr 2 O 3 ), aluminium oxide (Al 2 O 3 ), iron(III) oxide (Fe 2 O 3 ), iron(II) oxide (FeO), magnesium oxide (MgO), calcium oxide (CaO), silicon oxide (SiO 2 ), vanadium oxide (V 2 O 5 ), sodium oxide (Na 2 O) and sodium monochromate (Na 2 CrO 4 ).
- metal oxides such as chromium(III) oxide (Cr 2 O 3 ), aluminium oxide (Al 2 O 3 ), iron(III) oxide (Fe 2 O 3 ), iron(II) oxide (FeO), magnesium oxide (MgO), calcium oxide (CaO), silicon oxide (SiO 2 ), vanadium oxide (V 2 O 5 ), sodium oxide (Na 2 O) and sodium monochromate (Na 2 CrO 4 ).
- the Cr(VI) is preferably present as sodium monochromate (Na 2 CrO 4 ) in the COPR.
- the CaO content of the COPR is preferably less than 15% by weight, particularly preferably less than 10% by weight, most preferably less than 5% by weight.
- COPR preferably contains:
- the Cr(VI) content of the COPR is 0,01 - 1 weight-%.
- the Cr content in the COPR is 2 to 25 weight-%, particularly preferably 5 to 9 weight-%.
- the Fe content in the COPR is 28 to 35 weight-%, particularly preferably 29 to 34 weight-%.
- the Si content in the COPR is 0 to 1,5 weight-%, particularly preferably 0,4 to 1,0 weight-%.
- the Cr(VI) content of the COPR is preferably ⁇ 0,0001 weight-%.
- COPR with a Cr(VI) content of ⁇ 0,0001 weight-% is preferably obtained via a reduction process of COPR with a Cr(VI) content of 0,01 - 1 weight-% in that the reduction of Cr(VI) to Cr(III) takes preferably place via polyethylene glycol (PEG) or glycerol as disclosed in WO2014/006196 or, alternatively, in an atmosphere containing less than 0,1% by volume of an oxidizing gas as disclosed in WO 2016074878A1 .
- PEG polyethylene glycol
- glycerol as disclosed in WO2014/006196
- weight-% refer to the weight of the COPR.
- essentially no reductant carbonaceous reductants selected from anthracite, char, coke and bituminous coal are present in step a).
- the term "essentially no” is to be understood in the context of this application as an amount of less than 3 weight-%, preferably less than 2 weight-% more preferably less than 1 weight-% and most preferably 0 weight-% (i.e. not used at all) based on the amount of chrome ore material, COPR and reductant components.
- step a essentially no overall carbonaceous reductants are present in step a).
- overall carbonaceous reductants refers to anthracite, char, coke and bituminous but also to all organic substances, which are capable of reducing the Fe- or Cr-oxides in the chrome ore material under the sintering conditions of step c).
- step a essentially no overall reductant components are present in step a).
- overall reductant components includes all inorganic and organic, preferably organic substances, which are capable of reducing the Fe- or Cr oxides in the chrome ore material under the sintering conditions of step c).
- the amount of the reductants in the mixture obtained after the mixing in step a) or in the pellets obtained from step a) is not higher than the amount of reductant present in step a).
- Anthracite contains preferably less than 1 weight-% of organic compounds. Such organic compounds preferably evaporate at temperatures above 70°C up to 1400°C in an inert atmosphere. These organic compounds are preferably saturated and unsaturated hydrocarbons.
- the quantity of these organic compounds is determined by heating the reducing component in an inert atmosphere up to the target temperature and taking readings on the mass loss. This detected mass loss is subtracted from the mass loss found on heating the pellets in a second step, in order to calculate the degree of reduction.
- the mixing is conducted by using a dry ball mill.
- the solid components used in step a) are preferably milled.
- the milling can take place prior to the mixing in step a), during the mixing in step a) or after the mixing in step a).
- the chrome ore material, COPR and a reductant component are milled during mixing in step a).
- the mixture of the solids obtained after the mixing of the chrome ore material, COPR and an optional reductant component in step a), comprises:
- the mixture of the solids obtained after the mixing of the chrome ore material, COPR and an optional reductant component in step a), comprises
- the mixture obtained after the mixing of the chrome ore material, COPR and an optional reductant component in step a) provides a particle size distribution (d90) of 50 to 100 ⁇ m, particularly preferably of 65 to 85 ⁇ m.
- a d90 of 50 ⁇ m means that 90% by volume of the particles of the mixture have a particle size of 50 ⁇ m and below.
- the mixture obtained after the mixing of chrome ore material, COPR and an optional reductant component is further mixed with water.
- the pelletization takes place.
- palletization can be effected by pressing the mixture into the desired form.
- the weight ratio of water to the sum of the components chrome ore material, COPR and a reductant component is preferably between 1:6 and 1: >100, particularly preferably between 1:8 and 1: >100, most preferably 1: 125.
- the pelletization may take place in either a pan or drum pelletizing unit. Thereby, composite carbon containing (so called "green”) ore pellets are obtained.
- the ore pellets obtained after step a) have a diameter of 4-30 mm, more preferably 8-20 mm, most preferably of 10-15 mm.
- the diameter of a sphere having the same volume as the non-spherical pellet shall be regarded to constitute the diameter of the non-spherical pellet.
- the silicon content of the ore pellets obtained after step a) is below 2,5 weight-%, particularly preferably below 2 weight-%, whereas the weight-% refer to the weight of the ore pellets obtained after step a).
- the ore pellets obtained after step a) do not crack when dropped from a height of up to 0,2 m, particularly preferably of up to 0,4 m, most preferably of up to 0,5 m, on a steel plate.
- the green wet ore pellets show, after drying in air, a density higher then pellets produced with a binder state-of-the-art.
- the ore pellets can be pre-dried under ambient conditions, preferably at a temperature of 18 to 30°C, for 4 to 40 hours, preferably for 12 to 30 hours, but this is optional.
- the optional drying is done by heating the ore pellets under atmospheric conditions, preferably. Particularly preferably, the drying takes place at a temperature above 70°C, most preferably above 100°C.
- the time for the drying is preferably 2 to 50 hours, particularly preferably 6 to 30 hours, and can be performed in an oven.
- step b) The calcining of the ore pellets obtained after step a) or step b), if step b) is performed, may be conducted in different ways known to the skilled person.
- This sinter process can be performed either under ambient gas atmosphere or under an atmosphere with reduced oxygen level compared to ambient atmosphere.
- the heating unit is preferably a rotary kiln, a muffle furnace, a tube furnace or, preferably, a tunnel furnace.
- the wet or optionally dry, ore pellets obtained after step a) are exposed to temperatures of 1250°C to 1600°C, for periods of 1 minute to 8 hours, preferably of 1300°C to 1500°C for periods of 5 minutes to 5 hours.
- the inert atmosphere contains less than 0,1 vol-% of oxygen.
- the inert atmosphere is argon.
- the ore pellets can be cooled down, preferably to a temperature of 18 to 25°C.
- the pellets obtained after step c) are discharged, either via direct hot transfer to the smelting furnace or via controlled cooling of the calcined product, to yield cool, mechanically stable pellets.
- the Cr(VI) content is preferably ⁇ 0,0001 weight-%.
- the calcined pellets obtained after step c) provide increased mechanical stability compared to those obtained after step a).
- the calcined pellets can be further stored or transported, e.g. to an electric submerged arc furnace for the preparation of Ferrochrome.
- the sintered pellets obtained after step c) have a cold crushing strength of at least 50kgf/pellet and an average of about 100kgf/pellet. This value is determined in consideration of DIN EN 993-5 (2016) by placing a pellet between two steel plates arranged in parallel. With an hydraulic system, the plates are constantly moved towards each other and the pellet in the gap is squeezed. The applied force is measured continuously. The measurement is stopped, as soon as the applied force decreases while the plates are still moving towards each other (pellet has cracked). The maximum force measured in the described setup is calculated as an applied weight in kgf. 1 kgf are equivalent to 9.806650 N. In the present examples, the cold crushing strength is given the as average of 100 pellets of same size.
- the invention further provides iron- and chrome-containing pellets that contain:
- the iron- and chrome-containing pellets contain chrome as chrome(III)oxide (Cr 2 O 3 ) and as chrome metal, iron as iron(II) oxide (FeO) and iron(III) oxide (Fe 2 O 3 ) and as iron metal, and silicon as silicon oxide (SiO 2 ).
- the ratio of iron metal to iron(II,III) in the iron- and chrome-containing pellets is preferably ⁇ 1:2, particularly preferably ⁇ 1:10.
- the ratio of chrome metal to chrome(III) in the iron- and chrome-containing pellets is preferably ⁇ 1:2, particularly preferably ⁇ 1:10.
- the ratio of iron and chrome metal to iron(II,III) and chrome(III) in the iron- and chrome-containing pellets is preferably ⁇ 1:2, particularly preferably ⁇ 1:10.
- the Cr(VI) content is preferably ⁇ 0,0001 weight-%.
- the iron- and chrome-containing pellets are particularly preferably free of Cr(VI).
- the iron- and chrome-containing pellets have a diameter of 6-13 mm.
- the iron- and chrome-containing pellets according to the invention are obtained by the process for preparing iron- and chrome-containing pellets according to the invention.
- the invention further provides the use of iron- and chrome-containing pellets according to the invention for the preparation of Ferrochrome.
- the invention further provides a process for the preparation of Ferrochrome by using iron- and chrome-containing pellets according to the invention.
- the material was placed in a pelletization disc and water was sprayed on the surface while the disc was turning to produce small pellets of about 3mm, which were screened out and used as seed pellets for the actual pelletizing process.
- pellets with an diameter of above 11,2 mm were screened out and dried.
- the density of the dried pellets was determined using the displaced volume method.
- the pellets were calcined in a chamber furnace. The temperature was increased rapidly (within few minutes) to 1400°C and hold for 10 minutes. The pellets were then left to cool down to ambient temperature. The density of the indurated pellets was determined on 200 pellets by the volume of displacement method. The cold crushing strength (CCS) was determined using 200 indurated pellets produced as above.
- the material was placed in a pelletization disc and water was sprayed on the surface while the disc was turning to produce small pellets of about 3mm, which were screened out and used as seed pellets for the actual pelletizing process.
- pellets with an diameter of above 11,2 mm were screened out and dried.
- the density of the dried pellets was determined using the displaced volume method.
- the pellets were calcined in a chamber furnace. The temperature was increased rapidly (within few minutes) to 1400°C and hold for 10 minutes. The pellets were then left to cool down to ambient temperature. The density of the indurated pellets was determined on 200 pellets by the volume of displacement method. The cold crushing strength (CCS) was determined using 200 indurated pellets produced as above.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18196811.6A EP3628753B1 (de) | 2018-09-26 | 2018-09-26 | Verfahren zur herstellung von eisen- und chromhaltigen pellets |
ES18196811T ES2923938T3 (es) | 2018-09-26 | 2018-09-26 | Procedimiento para preparar gránulos que contienen hierro y cromo |
PL18196811.6T PL3628753T3 (pl) | 2018-09-26 | 2018-09-26 | Sposób przygotowania peletek zawierających żelazo i chrom |
PCT/EP2019/075450 WO2020064587A1 (en) | 2018-09-26 | 2019-09-23 | Process for preparing iron- and chrome-containing pellets |
Applications Claiming Priority (1)
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EP18196811.6A EP3628753B1 (de) | 2018-09-26 | 2018-09-26 | Verfahren zur herstellung von eisen- und chromhaltigen pellets |
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EP3628753A1 true EP3628753A1 (de) | 2020-04-01 |
EP3628753B1 EP3628753B1 (de) | 2022-05-04 |
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EP18196811.6A Active EP3628753B1 (de) | 2018-09-26 | 2018-09-26 | Verfahren zur herstellung von eisen- und chromhaltigen pellets |
Country Status (4)
Country | Link |
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EP (1) | EP3628753B1 (de) |
ES (1) | ES2923938T3 (de) |
PL (1) | PL3628753T3 (de) |
WO (1) | WO2020064587A1 (de) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816095A (en) * | 1972-03-09 | 1974-06-11 | Allied Chem | Method for recovering chromium values from chromite ore |
ZA200403429B (en) | 2004-05-06 | 2005-11-30 | Xstrata South Africa Pty Ltd | Process. |
WO2010103343A1 (en) * | 2009-03-10 | 2010-09-16 | Tata Steel (Kzn) (Pty) Limited | An improved process for production of high carbon ferrochrome (hcfecr) and charge chrome with the use of a new type of chromite ore agglomerates |
WO2014006196A1 (de) | 2012-07-06 | 2014-01-09 | Lanxess Deutschland Gmbh | Verfahren zur reduktion von sechswertigem chrom in oxidischen feststoffen |
WO2016074878A1 (de) | 2014-11-13 | 2016-05-19 | Lanxess Deutschland Gmbh | Verfahren zur reduktion von sechswertigem chrom in oxidischen feststoffen |
-
2018
- 2018-09-26 ES ES18196811T patent/ES2923938T3/es active Active
- 2018-09-26 PL PL18196811.6T patent/PL3628753T3/pl unknown
- 2018-09-26 EP EP18196811.6A patent/EP3628753B1/de active Active
-
2019
- 2019-09-23 WO PCT/EP2019/075450 patent/WO2020064587A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816095A (en) * | 1972-03-09 | 1974-06-11 | Allied Chem | Method for recovering chromium values from chromite ore |
ZA200403429B (en) | 2004-05-06 | 2005-11-30 | Xstrata South Africa Pty Ltd | Process. |
WO2010103343A1 (en) * | 2009-03-10 | 2010-09-16 | Tata Steel (Kzn) (Pty) Limited | An improved process for production of high carbon ferrochrome (hcfecr) and charge chrome with the use of a new type of chromite ore agglomerates |
WO2014006196A1 (de) | 2012-07-06 | 2014-01-09 | Lanxess Deutschland Gmbh | Verfahren zur reduktion von sechswertigem chrom in oxidischen feststoffen |
WO2016074878A1 (de) | 2014-11-13 | 2016-05-19 | Lanxess Deutschland Gmbh | Verfahren zur reduktion von sechswertigem chrom in oxidischen feststoffen |
Non-Patent Citations (4)
Title |
---|
DWARAPUDI ET AL: "Development of Cold Bonded Chromite Pellets for Ferrochrome Production in Submerged Arc Furnace", ISIJ INTERNATIONAL,, vol. 53, no. 1, 1 January 2013 (2013-01-01), pages 9 - 17, XP002773408, DOI: 10.2355/ISIJINTERNATIONAL.53.9 * |
MINERALS ENGINEERING, vol. 34, 2012, pages 55 - 62 |
SINGH V ET AL: "Study the effect of chromite ore properties on pelletisation process", INTERNATIONAL JOURNAL OF MINERAL PROCESSING, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 88, no. 1-2, 1 August 2008 (2008-08-01), pages 13 - 17, XP023440242, ISSN: 0301-7516, [retrieved on 20080422], DOI: 10.1016/J.MINPRO.2008.04.003 * |
TATHAVADKAR V D ET AL: "The soda-ash roasting of chromite minerals: Kinetics considerations", METALLURGICAL AND MATERIALS TRANSACTIONS B, SPRINGER-VERLAG, NEW YORK, vol. 32, no. 4, 1 August 2001 (2001-08-01), pages 593 - 602, XP019697245, ISSN: 1543-1916 * |
Also Published As
Publication number | Publication date |
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EP3628753B1 (de) | 2022-05-04 |
ES2923938T3 (es) | 2022-10-03 |
WO2020064587A1 (en) | 2020-04-02 |
PL3628753T3 (pl) | 2022-09-12 |
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