EP3377659B1 - Improved ilmenite smelting process - Google Patents
Improved ilmenite smelting process Download PDFInfo
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- EP3377659B1 EP3377659B1 EP16847594.5A EP16847594A EP3377659B1 EP 3377659 B1 EP3377659 B1 EP 3377659B1 EP 16847594 A EP16847594 A EP 16847594A EP 3377659 B1 EP3377659 B1 EP 3377659B1
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- European Patent Office
- Prior art keywords
- pellets
- ore
- reduction
- ilmenite
- reduced
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- 238000000034 method Methods 0.000 title claims description 47
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims description 43
- 238000003723 Smelting Methods 0.000 title claims description 21
- 239000008188 pellet Substances 0.000 claims description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000011946 reduction process Methods 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000002893 slag Substances 0.000 description 18
- 238000001465 metallisation Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 6
- 239000003830 anthracite Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004320 controlled atmosphere Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
- C22B1/242—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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
Definitions
- This invention relates to a consolidated process for the preparation of carbon-based ilmenite pellets, the solid-state reduction thereof, and the subsequent smelting thereof in an electric furnace.
- the smelting of ilmenite consumes substantial quantities of electrical energy. Additionally, the operability of the furnace can be hindered due to frothing effects.
- Feed to the smelting furnace is generally made up of raw ilmenite ore and a solid, carbonaceous reductant.
- Raw ilmenite in a particular process, is replaced by pre-reduced ilmenite pellets.
- the steps for the production process of the latter are to prepare ilmenite pellets using bentonite and to pre-reduce the pellets in a rotary kiln in the presence of a solid, carbonaceous reductant in excess.
- the smelting of the pre-reduced ilmenite pellets is thus carried out in an AC furnace.
- the TiO 2 slag produced in this way is, however, contaminated with the bentonite which is an inorganic binder.
- US 6 685 761 relates to a method of and apparatus for producing beneficiated titanium oxides.
- the method includes the steps of forming agglomerates using a binder such as cellulose or fibre of carbon-based materials and low grade titanium materials, containing iron and iron oxides, and pre-reducing the agglomerates with heat to produce pre-reduced agglomerates of titanium oxides and metallized carbon-containing iron. Subsequently the pre-reduced agglomerates are heated in a hearth furnace to complete the reduction of oxides of titanium and to complete the metallization of the carbon-containing iron. The molten agglomerate is discharged into an electric smelter to provide a molten iron product and beneficiated titanium oxide slag. The high carbon molten iron product is then purified.
- the method also provides for the inclusion of a binder in the agglomerate, e.g. cellulose fiber.
- An object of the present invention is to provide an alternative process for pre-reducing an ore essentially targeting the metallisation of iron oxides contained in the ore.
- the invention provides a method of preparing a pre-reduced ilmenite ore for smelting, wherein metal oxides contained in the ore are selectively reduced in solid-state reactions over titanium oxide, the method being characterised in that it includes the step of pre-reducing carbon-based pellets of the ore wherein the pellets are less than 6mm in size and are prepared from a blend of the ore, coal fines and an organic binder.
- the metal oxides, other than titanium oxides, in the pellets may be pre-reduced to a maximum extent i.e. essentially fully or they may be partially pre-reduced.
- the pellets may be in a range of 2mm to 5mm.
- the coal fines used to prepare the pellets may be of -106 microns.
- the ratio of the coal to the metallic oxide content may be practically determined. For example a stoichiometric ratio for the full reduction of iron in the ore can be used.
- the organic binder content may lie in the range of 0 to 1%. This content may be dictated by the physical properties of the resulting pellets principally the strength of the pellets in a green state and in an air-dried or indurated state.
- the pellets may be may be air-indurated for at least 4 days. This period is usually adequate to ensure that the pellets are sufficiently strong to allow their safe and efficient handling to subsequent pre-reduction reactors.
- the mechanical strength of the pellets is preferably above 600N.
- the pellets should also have an acceptable behaviour in a hot reactor environment to avoid decrepitation due to excessive swelling.
- a single binder or a mixture of binders may be used.
- the invention is not limited in this respect.
- Pre-reduced pellets are evaluated based on the reduction extent of iron oxides contained in the ore.
- the iron oxide should be present in a quantity of less than 10% from the initial content.
- a consistent pre-reduction yield should be a main target during a normal and stable operation.
- the pellets may be subjected to a thermal reduction process or to a hybrid, solid-state, reduction process.
- the pellets, air-dried and indurated, may be heated in a fixed bed reactor at an optimal residence time which may lie in a range of from 0.5 to 4 hours.
- the pellets may be heated at a temperature in the range of 1100 to 1200°C.
- the pellets may be heated to a temperature in the range of 900 to 1000°C in a controlled atmosphere of a reducing gas.
- the reducing gas may comprise one or more of the following: CO, syngas (CO + H 2 ), natural gas and hydrogen.
- the reducing gas may be filtered through a hot burden in the reactor.
- the reducing gas flowrate should be selected to achieve an adequate reduction yield of the iron oxides in the ore, as well as acceptable reactor operation performance.
- the invention finds particular application in the preparation of pre-reduced, carbon-based, ilmenite micro-pellets which are to be smelted e.g. in a DC open arc furnace.
- the principles of the invention may be employed for the pre-reduction of pellets of titaniferous magnetite, ferrochrome and ferromanganese ores for the subsequent production of titania slag, chrome and manganese, alloys respectively.
- the invention is hereinafter described with reference to the pre-reduction of carbon-based, ilmenite, micro-pellets. Although this is a preferred application of the principles of the invention it is possible to adapt the principles described herein for the pre-reduction of titaniferous magnetite, ferrochrome and ferromanganese ores.
- Raw ilmenite ore 10 of a suitable size is fed to a blender 12.
- the blender also receives coal fines 14 of -106 micron in size and an organic binder 16 formed from a single binder or from a mixed binder composition.
- the ratio of the input coal to the ilmenite is determined taking into account practical considerations. For instance a stoichiometric ratio which achieves a full reduction of iron in the ilmenite ore can be used. Further, the input of organic binder or mixes of organic binders, in the range of up to 1%, is dictated by the physical properties of the resulting pellets, particularly the green and air-dried strengths of the pellets. The resulting pellets should also have an acceptable behaviour (subsequently) in a hot reactor environment to avoid decrepitation due to excessive swelling.
- the blender 12 produces carbon-based, ilmenite, micro-pellets of 2mm to 5mm in size. These pellets are then air-dried (step 20).
- the air-dried, indurated pellets are then subjected to a thermal pre-reduction step 22, or to a hybrid, solid-state pre-reduction step 24.
- the air-dried indurated pellets are heated in a fixed bed reactor 26 for an optimal residence time, generally from 0.5 to 4 hours.
- the pellets are heated in the reactor 26 to a temperature in the range of 1100 to 1200°C. If use is made of the hybrid approach then the pellets are heated in the reactor 26 to a temperature of 900 to 1000°C in a controlled atmosphere of a reducing gas 30 which comprises one or more of CO, syngas, natural gas and hydrogen.
- the reducing gas is filtered through the hot burden of the pellets in the reactor 26.
- the reducing gas flowrate is regulated to achieve an adequate pre-reduction yield.
- the flowrate should also be regulated to optimise the reactor operation, principally the thermal efficiency and the production cost.
- Process parameters of importance include: the ilmenite grain size distribution, the composition of the pellets, the sizes of the pellets, the operating temperature, the residence time and the reducing gas flowrate.
- each method is able to produce a consistent pre-reduction yield.
- the hybrid method despite operating at a lower temperature then the thermal reduction method, appears to offer a higher pre-reduction yield than the thermal method.
- the fully or partially pre-reduced ilmenite pellets 32, emerging from the reactor 26, can be fed, cold or hot, to a conventional ilmenite smelting process 36.
- the organic binder provides a more intimate contact between the ilmenite and the coal fines.
- the small pellet size feature in a highly reducing atmosphere, assists the transfer of heat and mass in the diffusion of gaseous reductants, such as CO and H 2 , to the reaction sites.
- the organic binder 16 burns off at the process temperature, a feature which induces localised reduction and promotes the formation of cracks and pores in the ilmenite ore grains contained in the pellets 32.
- the specific surface areas of the ilmenite pellets are therefore increased and the diffusion rate of the gas reductant to the reaction sites is enhanced. This in turn impacts on the pre-reduction yield.
- the reduction process can be smoothly and efficiently operated despite the minor sintering of the pellets that may occur at elevated temperatures.
- the fully or partially pre-reduced, carbon-based ilmenite pellets which are fed, either hot or cold, into a DC open arc furnace decrease the consumption of electricity in the furnace, help to address slag foaming and result in an improved grade of TiO 2 slag 38 output by the furnace.
- the use of the thermal pre-reduction process at a temperature of 1100 to 1200°C produced a pre-reduction yield of about 85% - a value which is adversely affected with an increase in ilmenite ore grain size and with an increase in the size of the coal fines.
- a higher grade TiO 2 slag (above 90%) can thus be achieved, using conventional ilmenite feedstock in smelting operations, with no foaming occurring.
- a lower grade ilmenite could be used as feedstock to produce TiO 2 slag of at least 85% TiO 2 content.
- the invention has been described with reference to the use of a gaseous reductant. It is possible though to make use of a solid reductant such as anthracite or coal, instead of the reducing gas 30. Also the reactor 26 which, typically, is a fixed bed reactor can be replaced by a moving bed or by a rotary kiln configuration provided abrasion effects between the pellets are minimised. It should be possible though to separate the pre-reduced pellets, for example using magnetic techniques, from the other material emerging from the reactor.
- a solid reductant such as anthracite or coal
- Additional carbonaceous solid reductant can be used in excess to reduce residual iron in the slag to below 6% without inducing slag foaming.
- a 200 kW DC arc furnace facility was used for demonstrating the smelting of pre-reduced ilmenite pellets.
- the furnace had a 1 m outer diameter, water-spray cooled steel shell lined with a single layer and three rows of magnesite-chrome bricks and a hearth lined with rammable magnesia.
- the refractory lining resulted in the furnace crucible internal diameter (ID) of 0.656 m.
- ID furnace crucible internal diameter
- the furnace was equipped with an alumina lined conical roof and a shell bolted on a domed base. A single taphole was used to tap a stream of both molten slag and metal.
- the furnace was equipped with a single and centrally-located graphite electrode of 40 mm diameter operating as a cathode while the anode comprised steel pins buried in the hearth.
- the feed system comprised individual hoppers used to feed anthracite and pre-reduced ilmenite pellets through a furnace feed pipe.
- the furnace was equipped with an off-gas system for the cleaning of produced process gas prior to release thereof into the atmosphere.
- the as-received ilmenite had a particle size distribution of D 100 in the 38 ⁇ m to 150 ⁇ m size range.
- the anthracite was milled to a D 85 passing 106 ⁇ m to facilitate its incorporation into an ilmenite pellet recipe.
- Pellets were prepared in a pilot-scale pelletizing unit comprising an inclined rotating pan of 985 mm diameter and 170 mm depth. The mechanical strengths of the pellets were measured and found to vary with the type and dosage of binder used, within a range of 0.01 - 0.03 MPa for green pellets and 0.81 - 1.50 MPa for indurated pellets at ambient conditions.
- Table 1 The chemical analyses of the ore and anthracite are summarised in Table 1 and Table 2, respectively.
- Table 1 Bulk chemical composition of the raw ilmenite (mass %) MgO Al 2 O 3 SiO 2 CaO TiO 2 V 2 O 5 Cr 2 O 3 MnO FeO Fe 2+ Fe 0 Fe/Ti 0.28 0.44 0.57 0.05 46.6 0.25 0.09 1.08 47.87 13.50 ⁇ 0.05 1.33 ⁇ 0.05%: the analyte concentration could not be accurately quantified as it is below the limit of detection (LOD) Total Fe in the sample is expressed as % FeO Table 2: Summary of the bulk chemical composition of the anthracite (mass %) Moisture Ash Volatile Fixed carbon Total carbon Total sulphur 3.57 4.74 6.19 89.1 90.7 0.56
- Tables 3 and 4 show that pellets prereduced to a consistent extent were produced as a result of the uniform furnace operating conditions.
- Table 5 Analysis of slag from the stable smelting operation, in mass % Tap *TiO 2 CT 2 O 3 MnO FeO V 2 O 5 SiO 2 CaO Al 2 O 3 MgO A 84.74 1,34 1,37 2,06 0,30 1,31 0,34 1,96 6,58 B 87.84 0,60 1,18 2,59 0,21 1,16 0,28 2,49 3,65 C 83.15 0,31 1,68 2,73 0,29 1,20 0,38 2,76 7,50 D 88.86 0,45 0,68 4,89 0,17 0,49 0,31 1,45 2,70 E 88.19 0,45 0,99 4,37 0,16 0,43 0,35 1,53 3,53 F 91.27 0,31 1,47 1,58 0,15 0,28 0,32 1,47 3,15 G 94.28 0,08 1,32 1,25 0,10 0,21 0,17 0,98 1,61 H 93.32 0,09 1,21 1,48 0,10 0,16 0,14 1,10 2,40 *by difference Table 6: Evolution of composition of pig iron from the stable smelting operation, in mass % Tap Fe Ti V Si Cr Mn C
- the 200 kW DC open-arc furnace was operated at a power level in the range of 115 - 140 kW and at a corresponding voltage of 100 - 115 V. Consistent furnace heat losses in the range of 60 - 90 kW were measured. Average tapping temperatures measured using an optical pyrometer were scattered within a range between 1670 and 1780°C. The specific energy requirement (SER) for the smelting of prereduced carbon-based pellets was measured between 0.6 and 0.7 kWh / kg prereduced ilmenite. A 30-40 % reduction in furnace electricity required relative to a conventional smelting process can be achieved assuming that a prereduction yield of at least 70 % can be achieved.
- SER specific energy requirement
- Arc resistivities were measured for various conditions investigated in order to predict the furnace arc stability. Arc resistivity was found to be in the range of 0.0168 and 0.0240 ⁇ .cm which range is close to 0.0175 ⁇ .cm, a typical value for arc resistivity in smelting processes with CO-rich atmospheres (in the absence of foaming).
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Description
- This invention relates to a consolidated process for the preparation of carbon-based ilmenite pellets, the solid-state reduction thereof, and the subsequent smelting thereof in an electric furnace.
- The smelting of ilmenite consumes substantial quantities of electrical energy. Additionally, the operability of the furnace can be hindered due to frothing effects.
- Feed to the smelting furnace is generally made up of raw ilmenite ore and a solid, carbonaceous reductant. Raw ilmenite, in a particular process, is replaced by pre-reduced ilmenite pellets. The steps for the production process of the latter are to prepare ilmenite pellets using bentonite and to pre-reduce the pellets in a rotary kiln in the presence of a solid, carbonaceous reductant in excess. The smelting of the pre-reduced ilmenite pellets is thus carried out in an AC furnace. The TiO2 slag produced in this way is, however, contaminated with the bentonite which is an inorganic binder.
-
US 6 685 761 relates to a method of and apparatus for producing beneficiated titanium oxides. The method includes the steps of forming agglomerates using a binder such as cellulose or fibre of carbon-based materials and low grade titanium materials, containing iron and iron oxides, and pre-reducing the agglomerates with heat to produce pre-reduced agglomerates of titanium oxides and metallized carbon-containing iron. Subsequently the pre-reduced agglomerates are heated in a hearth furnace to complete the reduction of oxides of titanium and to complete the metallization of the carbon-containing iron. The molten agglomerate is discharged into an electric smelter to provide a molten iron product and beneficiated titanium oxide slag. The high carbon molten iron product is then purified. The method also provides for the inclusion of a binder in the agglomerate, e.g. cellulose fiber. - An object of the present invention is to provide an alternative process for pre-reducing an ore essentially targeting the metallisation of iron oxides contained in the ore.
- The invention provides a method of preparing a pre-reduced ilmenite ore for smelting, wherein metal oxides contained in the ore are selectively reduced in solid-state reactions over titanium oxide, the method being characterised in that it includes the step of pre-reducing carbon-based pellets of the ore wherein the pellets are less than 6mm in size and are prepared from a blend of the ore, coal fines and an organic binder.
- The metal oxides, other than titanium oxides, in the pellets may be pre-reduced to a maximum extent i.e. essentially fully or they may be partially pre-reduced.
- The pellets may be in a range of 2mm to 5mm.
- The coal fines used to prepare the pellets may be of -106 microns.
- The ratio of the coal to the metallic oxide content may be practically determined. For example a stoichiometric ratio for the full reduction of iron in the ore can be used.
- The organic binder content may lie in the range of 0 to 1%. This content may be dictated by the physical properties of the resulting pellets principally the strength of the pellets in a green state and in an air-dried or indurated state. The pellets may be may be air-indurated for at least 4 days. This period is usually adequate to ensure that the pellets are sufficiently strong to allow their safe and efficient handling to subsequent pre-reduction reactors. The mechanical strength of the pellets is preferably above 600N. The pellets should also have an acceptable behaviour in a hot reactor environment to avoid decrepitation due to excessive swelling.
- A single binder or a mixture of binders may be used. The invention is not limited in this respect.
- Pre-reduced pellets are evaluated based on the reduction extent of iron oxides contained in the ore. Preferably the iron oxide should be present in a quantity of less than 10% from the initial content. However a consistent pre-reduction yield should be a main target during a normal and stable operation.
- The pellets may be subjected to a thermal reduction process or to a hybrid, solid-state, reduction process.
- The pellets, air-dried and indurated, may be heated in a fixed bed reactor at an optimal residence time which may lie in a range of from 0.5 to 4 hours.
- If a thermal pre-reduction step is adopted then the pellets may be heated at a temperature in the range of 1100 to 1200°C.
- If the hybrid, solid-state, pre-reduction step is adopted then the pellets may be heated to a temperature in the range of 900 to 1000°C in a controlled atmosphere of a reducing gas.
- The reducing gas may comprise one or more of the following: CO, syngas (CO + H2), natural gas and hydrogen.
- If a fixed bed reactor is employed then the reducing gas may be filtered through a hot burden in the reactor. The reducing gas flowrate should be selected to achieve an adequate reduction yield of the iron oxides in the ore, as well as acceptable reactor operation performance.
- The invention finds particular application in the preparation of pre-reduced, carbon-based, ilmenite micro-pellets which are to be smelted e.g. in a DC open arc furnace. However, the principles of the invention may be employed for the pre-reduction of pellets of titaniferous magnetite, ferrochrome and ferromanganese ores for the subsequent production of titania slag, chrome and manganese, alloys respectively.
- Reference has been made to heating the air-dried pellets in a fixed bed reactor. This is exemplary only and non-limiting. A moving bed and a rotary kiln may be employed in place of the fixed bed reactor, in a pre-reduction stage. It is important that abrasion of the pellets is minimised and it should be possible to separate pre-reduced fines from other material, for example through the use of magnetic or equivalent techniques.
- The invention is further described by way of example with reference to the accompanying figures wherein;
-
Figure 1 illustrates in flow chart form the pre-reduction of carbon-based, ilmenite micro-pellets and the subsequent smelting thereof; -
Figure 2 is a diagram depicting an impact of the residence time on pre-reduction and metallisation degrees at 1000°C and 0.5l CO / min; and -
Figure 3 is a diagram depicting an impact of the CO flowrate on the pre-reduction and metallisation degrees at 1000°C and 1h residence time. - The invention is hereinafter described with reference to the pre-reduction of carbon-based, ilmenite, micro-pellets. Although this is a preferred application of the principles of the invention it is possible to adapt the principles described herein for the pre-reduction of titaniferous magnetite, ferrochrome and ferromanganese ores.
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Raw ilmenite ore 10 of a suitable size is fed to ablender 12. The blender also receivescoal fines 14 of -106 micron in size and anorganic binder 16 formed from a single binder or from a mixed binder composition. - The ratio of the input coal to the ilmenite is determined taking into account practical considerations. For instance a stoichiometric ratio which achieves a full reduction of iron in the ilmenite ore can be used. Further, the input of organic binder or mixes of organic binders, in the range of up to 1%, is dictated by the physical properties of the resulting pellets, particularly the green and air-dried strengths of the pellets. The resulting pellets should also have an acceptable behaviour (subsequently) in a hot reactor environment to avoid decrepitation due to excessive swelling.
- The
blender 12 produces carbon-based, ilmenite, micro-pellets of 2mm to 5mm in size. These pellets are then air-dried (step 20). - The air-dried, indurated pellets are then subjected to a thermal
pre-reduction step 22, or to a hybrid, solid-state pre-reductionstep 24. In each instance the air-dried indurated pellets are heated in afixed bed reactor 26 for an optimal residence time, generally from 0.5 to 4 hours. - If use is made of the thermal pre-reduction process the pellets are heated in the
reactor 26 to a temperature in the range of 1100 to 1200°C. If use is made of the hybrid approach then the pellets are heated in thereactor 26 to a temperature of 900 to 1000°C in a controlled atmosphere of a reducinggas 30 which comprises one or more of CO, syngas, natural gas and hydrogen. The reducing gas is filtered through the hot burden of the pellets in thereactor 26. The reducing gas flowrate is regulated to achieve an adequate pre-reduction yield. The flowrate should also be regulated to optimise the reactor operation, principally the thermal efficiency and the production cost. - Process parameters of importance, in respect of the of pre-reduction technique used, include: the ilmenite grain size distribution, the composition of the pellets, the sizes of the pellets, the operating temperature, the residence time and the reducing gas flowrate.
- Taken under consistent operating conditions each method is able to produce a consistent pre-reduction yield. The hybrid method, despite operating at a lower temperature then the thermal reduction method, appears to offer a higher pre-reduction yield than the thermal method.
- The fully or partially
pre-reduced ilmenite pellets 32, emerging from thereactor 26, can be fed, cold or hot, to a conventionalilmenite smelting process 36. - Without being bound by the following explanation it is believed that the organic binder provides a more intimate contact between the ilmenite and the coal fines. The small pellet size feature, in a highly reducing atmosphere, assists the transfer of heat and mass in the diffusion of gaseous reductants, such as CO and H2, to the reaction sites. The
organic binder 16 burns off at the process temperature, a feature which induces localised reduction and promotes the formation of cracks and pores in the ilmenite ore grains contained in thepellets 32. The specific surface areas of the ilmenite pellets are therefore increased and the diffusion rate of the gas reductant to the reaction sites is enhanced. This in turn impacts on the pre-reduction yield. The reduction process can be smoothly and efficiently operated despite the minor sintering of the pellets that may occur at elevated temperatures. - The fully or partially pre-reduced, carbon-based ilmenite pellets which are fed, either hot or cold, into a DC open arc furnace decrease the consumption of electricity in the furnace, help to address slag foaming and result in an improved grade of TiO2 slag 38 output by the furnace.
- Through tests it has been established that iron oxide in the pellets was nearly completely reduced through the use of the hybrid pre-reduction process carried out at a temperature of 1000°C and for a residence time of 2 hours. The pre-reduction yield was increased as temperature, residence time and reducing gas flowrate were increased.
- The use of the thermal pre-reduction process at a temperature of 1100 to 1200°C produced a pre-reduction yield of about 85% - a value which is adversely affected with an increase in ilmenite ore grain size and with an increase in the size of the coal fines.
- About 4 tons of cold pre-reduced ilmenite pellets were smelted in a DC open arc furnace. The energy consumption of the furnace lay in the range of 0.6 to 0.7 kWh / kg of pre-reduced ilmenite pellets - a figure which represents an electrical energy saving of 30 to 40% compared to a conventional ilmenite smelting process. The smelting process was stable with no visible sign of foaming. The product contained about 95% TiO2 and about 3% FeO.
- A higher grade TiO2 slag (above 90%) can thus be achieved, using conventional ilmenite feedstock in smelting operations, with no foaming occurring. Using the method of the current invention, a lower grade ilmenite could be used as feedstock to produce TiO2 slag of at least 85% TiO2 content.
- The invention has been described with reference to the use of a gaseous reductant. It is possible though to make use of a solid reductant such as anthracite or coal, instead of the reducing
gas 30. Also thereactor 26 which, typically, is a fixed bed reactor can be replaced by a moving bed or by a rotary kiln configuration provided abrasion effects between the pellets are minimised. It should be possible though to separate the pre-reduced pellets, for example using magnetic techniques, from the other material emerging from the reactor. - Additional carbonaceous solid reductant can be used in excess to reduce residual iron in the slag to below 6% without inducing slag foaming.
- A 200 kW DC arc furnace facility was used for demonstrating the smelting of pre-reduced ilmenite pellets. The furnace had a 1 m outer diameter, water-spray cooled steel shell lined with a single layer and three rows of magnesite-chrome bricks and a hearth lined with rammable magnesia. The refractory lining resulted in the furnace crucible internal diameter (ID) of 0.656 m. The furnace was equipped with an alumina lined conical roof and a shell bolted on a domed base. A single taphole was used to tap a stream of both molten slag and metal. The furnace was equipped with a single and centrally-located graphite electrode of 40 mm diameter operating as a cathode while the anode comprised steel pins buried in the hearth. The feed system comprised individual hoppers used to feed anthracite and pre-reduced ilmenite pellets through a furnace feed pipe. The furnace was equipped with an off-gas system for the cleaning of produced process gas prior to release thereof into the atmosphere.
- Carbon-based ilmenite pellets containing the as received ilmenite, stoichiometric amount of anthracite, were prepared using a proprietary organic binder at a required dosage. The as-received ilmenite had a particle size distribution of D100 in the 38 µm to 150 µm size range. The anthracite was milled to a D85 passing 106 µm to facilitate its incorporation into an ilmenite pellet recipe. Pellets were prepared in a pilot-scale pelletizing unit comprising an inclined rotating pan of 985 mm diameter and 170 mm depth. The mechanical strengths of the pellets were measured and found to vary with the type and dosage of binder used, within a range of 0.01 - 0.03 MPa for green pellets and 0.81 - 1.50 MPa for indurated pellets at ambient conditions.
- Batches of 250 kg each of indurated pellets were reduced in an electrically heated muffle furnace operated at a controlled temperature of 1100 °C. During a three hour firing time, in total 5 kg of CO was blown intermittently through the reactor burden at intervals of 10 minutes. The pellets were loaded in a single tray of 1700 mm x 900 mm, having a loading area of a mesh screen acting as a distribution plenum for the reducing gas.
- Both the raw and pre-reduced ilmenite materials at various conditions were chemically analysed; specifically an analysis of the iron oxidation states (Fe3+, Fe2+, and Fe0) was used to calculate the pre-reduction and metallisation yields for the pellets. Negligible reduction of titanium oxides was assumed throughout and the pre-reduction yield was therefore calculated based on the mass balance of oxygen associated with each gram of iron before and after pre-reduction. Equations [1] and [2] were used for the calculation of the prereduction and metallization yields, respectively.
- The chemical analyses of the ore and anthracite are summarised in Table 1 and Table 2, respectively.
Table 1: Bulk chemical composition of the raw ilmenite (mass %) MgO Al2O3 SiO2 CaO TiO2 V2O5 Cr2O3 MnO FeO Fe2+ Fe0 Fe/Ti 0.28 0.44 0.57 0.05 46.6 0.25 0.09 1.08 47.87 13.50 <0.05 1.33 <0.05%: the analyte concentration could not be accurately quantified as it is below the limit of detection (LOD) Total Fe in the sample is expressed as % FeO Table 2: Summary of the bulk chemical composition of the anthracite (mass %) Moisture Ash Volatile Fixed carbon Total carbon Total sulphur 3.57 4.74 6.19 89.1 90.7 0.56 - In total, about 3.6 tons of pre-reduced pellets were produced. The pellets were bagged in 1 m3 bags from which five composite samples were collected. The chemical analyses of the 5 composite samples are given in Table 3.
Table 3: Chemical compositions of the pre-reduced pellets MgO Al2O3 SiO2 CaO TiO2 V2O5 Cr2O3 MnO Total Fe Fe0 Fe2+ C Ti3+ Fe/Ti ratio TP Bag 1 0.53 0.33 0.31 0.10 44.4 0.36 0.07 1.05 34.92 25.55 9.37 7.23 6.55 1.32 TP Bag 2 0.55 0.30 0.26 0.07 44.5 0.36 0.08 1.06 35.23 25.44 9.79 7.72 6.76 1.32 TP Bag 3 0.50 0.30 0.24 0.15 43.5 0.33 0.07 1.03 33.60 21.90 11.7 7.97 5.45 1.29 TP Bag 4 0.48 0.32 0.39 0.11 42.4 0.33 0.07 1.05 34.46 22.66 11.8 8.01 4.78 1.35 TP Bag 5 0.36 0.45 0.64 0.18 41.9 0.33 0.07 1.08 36.01 24.21 11.8 7.20 4.66 1.43 Average 0.48 0.34 0.37 0.12 43.3 0.34 0.07 1.05 34.84 23.95 10.8 9 7.63 5.64 1.32 St dev 0.07 0.06 0.16 0.04 1.17 0.02 0.004 0.02 0.90 1.64 1.21 0.39 0.98 0.02 - The calculated degrees of prereduction and metallization for the five composite samples are presented in Table 4
Table 4: Pre-reduction and metallisation degrees of ilmenite pellets Composite sample no. Pre-reduction degree, % Metallisation degree, % 1 79.7 73.2 2 78.9 72.2 3 73.6 65.2 4 74.1 65.8 5 75.1 67.2 Average 76.3 68.7 St dev 2.8 3.7 - Tables 3 and 4 show that pellets prereduced to a consistent extent were produced as a result of the uniform furnace operating conditions.
- Results from laboratory tests in a tube reactor of 80 mm diameter showed a very important feature of this process that is presented in
Figures 2 and3 . Tests conducted at a temperature of 1000°C, showed that pre-reduction and metallisation degrees are both related to the residence time and CO flowrate. Increasing the CO flowrate appears to positively affect the yields, suggesting that CO diffusion would play a significant role in this process. - Continuous smelting of partially reduced ilmenite pellets (approx.. 70% prereduction yield) was carried out to demonstrate stable furnace operation as well as production of a consistent slag quality, in particular, a slag TiO2 grade above 85%. The test work also had the objective of confirming the process specific energy requirement. The slag results are presented in Table 5.
Table 5: Analysis of slag from the stable smelting operation, in mass % Tap *TiO2 CT2O3 MnO FeO V2O5 SiO2 CaO Al2O3 MgO A 84.74 1,34 1,37 2,06 0,30 1,31 0,34 1,96 6,58 B 87.84 0,60 1,18 2,59 0,21 1,16 0,28 2,49 3,65 C 83.15 0,31 1,68 2,73 0,29 1,20 0,38 2,76 7,50 D 88.86 0,45 0,68 4,89 0,17 0,49 0,31 1,45 2,70 E 88.19 0,45 0,99 4,37 0,16 0,43 0,35 1,53 3,53 F 91.27 0,31 1,47 1,58 0,15 0,28 0,32 1,47 3,15 G 94.28 0,08 1,32 1,25 0,10 0,21 0,17 0,98 1,61 H 93.32 0,09 1,21 1,48 0,10 0,16 0,14 1,10 2,40 *by difference Table 6: Evolution of composition of pig iron from the stable smelting operation, in mass % Tap Fe Ti V Si Cr Mn C P S A 95.54 0.67 0.24 0.34 1.04 0.48 1.66 0.02 0.01 B 95.92 0.43 0.23 0.36 1.08 0.44 1.53 0.00 0.01 C 95.15 0.55 0.16 0.38 1.47 0.33 1.92 0.02 0.02 D 97.03 0.16 0.09 0.18 0.52 0.21 1.76 0.02 0.03 E 94.59 0.29 0.20 0.62 1.14 0.51 2.57 0.03 0.05 F 91.81 3.64 0.23 0.64 1.17 0.86 1.62 0.01 0.02 G 95.83 0.57 0.20 0.41 0.71 0.60 1.64 0.02 0.02 H 93.66 1.34 0.32 1.28 0.89 0.88 1.56 0.02 0.05 - Slag FeO contents as low as 1.3 % were achieved without visible signs of slag foaming. This condition was maintained for a longer period during which stable furnace operation was demonstrated and slags of consistent FeO content were produced. Results for this particular test work suggest that smelting of partially reduced ilmenite and operating the furnace with lower FeO content in the slag are technically possible.
- The 200 kW DC open-arc furnace was operated at a power level in the range of 115 - 140 kW and at a corresponding voltage of 100 - 115 V. Consistent furnace heat losses in the range of 60 - 90 kW were measured. Average tapping temperatures measured using an optical pyrometer were scattered within a range between 1670 and 1780°C. The specific energy requirement (SER) for the smelting of prereduced carbon-based pellets was measured between 0.6 and 0.7 kWh / kg prereduced ilmenite. A 30-40 % reduction in furnace electricity required relative to a conventional smelting process can be achieved assuming that a prereduction yield of at least 70 % can be achieved. Arc resistivities were measured for various conditions investigated in order to predict the furnace arc stability. Arc resistivity was found to be in the range of 0.0168 and 0.0240 Ω.cm which range is close to 0.0175 Ω.cm, a typical value for arc resistivity in smelting processes with CO-rich atmospheres (in the absence of foaming).
Claims (17)
- A method of preparing a pre-reduced ilmenite ore (32) for smelting (36) wherein metal oxides, contained in the ore are selectively reduced in solid-state reactions over titanium oxide, the method includes the step of pre-reducing (22 and 24) carbon-based pellets (21) of the ore, wherein the pellets are less than 6mm in size and are prepared from a blend of the ore (10), coal fines (14) and an organic binder (16).
- A method according to claim 1 characterised in that the metal oxides, other than titanium oxides, in the pellets are pre-reduced to a maximum extent.
- A method according to claim 1 characterised in that the pellets are between 2mm and 5mm in size.
- A method according to claim 1 characterised in that the coal fines (14) have a size of -106 microns.
- A method according to any one of claims 1 to 4 characterised in that the ratio of the coal to the metallic oxide content is determined using a stoichiometric ratio for the full reduction of iron in the ore.
- A method according to any one of claims 1 to 5 characterised in that the organic binder (16) content is in the range of 0 to 1%.
- A method according to any one of claims 1 to 6 characterised in that a single organic binder (16) or a mixture of organic binders (16) is used.
- A method according to any one of claims 1 to 7 characterised in that the pellets are air indurated (20) for at least 4 days.
- A method according to claim 8 characterised in that a mechanical strength of the pellets (21) is of the order of 600N.
- A method according to any one of claims 1 to 9 characterised in that iron oxide in the ore (10) is present in a quantity of less than 10%.
- A method according to any one of claims 1 to 10 characterised in that the pellets are subjected to a thermal reduction process (22) or to a hybrid, solid-state, reduction process (24).
- A method according to claim 11 characterised in that the pellets are heated in a fixed bed reactor (26) for a time period of between 0.5 to 4 hours.
- A method according to claim 12 characterised in that a thermal pre-reduction step (22) is adopted and the pellets (21) are heated to a temperature in the range of 1100 to 1200°C.
- A method according to claim 11 or 12 characterised in that a hybrid, solid-state, pre-reduction step 24 is adopted and the pellets (21) are heated to a temperature in the range of 900 to1000°C.
- A method according to claim 14 characterised in that a reducing gas (30) is filtered through a hot burden in the fixed bed reactor (26).
- A method according to claim 15 characterised in that the reducing gas (30) comprises one or more of the following: carbon monoxide; syngas (CO+H2); natural gas; and hydrogen.
- A method according to any one of claims 1 to 16 characterised in that the smelting is conducted in a DC open arc furnace at a temperature of between 1650 and 1750°C.
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