METHOD AND APPARATUS FOR PRODUCING METALLIC IRON FROM IRON OXIDE FINES
20180221947 ยท 2018-08-09
Assignee
Inventors
Cpc classification
C21B13/0086
CHEMISTRY; METALLURGY
Y02P20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C21B13/0026
CHEMISTRY; METALLURGY
B22F3/001
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
C21B13/0073
CHEMISTRY; METALLURGY
Y02P10/143
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P10/134
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B22F3/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Method and apparatus for producing direct reduced iron (DRI) powder or molten iron from iron ore fines by mixing said iron ore fines with hydrogen and oxygen and igniting the mixture in a flame reactor with flame temperatures controlled to produce solid iron powder or molten iron.
Claims
1. A process for producing metallic iron from iron oxide fines, the process comprising: a) introducing a stream of a reducing gas into the feed pipe entering an In-Flight reactor (IFR), b) introducing iron oxide fines into the said feed pipe, c) introducing a stream of an internal heating gas into the said feed pipe, d) feeding a separate stream of an oxidizing gas into the said In-Flight reactor, e) delivering the mixed iron oxide, reducing gas, heat generating gas and the oxidizing gas into a reducing reaction flame through a burner nozzle, f) forming hot metallic iron entrained in a hot exhaust gas, and g) separating the said hot metallic iron and hot exhaust gas in an In-Flight Separation Unit (IFSU).
2. The process according to claim 1 wherein the said In-Flight reactor may be water cooled.
3. The process according to claim 1 wherein the said internal heating gas comprises hydrogen and oxygen generated by the electrolysis of water in an electrolyzer,
4. The process according to claim 1 wherein the said internal heating gas is natural gas,
5. The process according to claim 1 wherein the said reducing gas is natural gas,
6. The process according to claim 1 wherein the said iron oxide fines are mixed with slag forming materials to generate a slag suitable for manufacturing slag cement.
7. The process according to claim 1 wherein the said In-Flight reactor is mounted in a tangential inlet port in the said IFSU.
8. The process according to claim 1 wherein multiple In-Flight reactors are mounted in the tangential inlet ports of the said IFSU
9. The process according to claim 1 wherein the said IFSU has a removable, refractory lined top containing a central vortex finder.
10. The process according to claim 1 wherein the said IFSU has a refractory lined main body with an upper cylindrical section and a lower conical section with an apex orifice.
11. The process according to claim 1 wherein the said IFSU can be fitted with a removable refractory lined crucible for collecting molten products.
12. The process according to claim 1 wherein the said IFSU can be fitted with a removable refractory lined hopper for retaining fine solids.
13. The process according to claim 11 wherein the said crucible has means to permit tapping of the said molten products.
14. The process according to claim 11 wherein one of the molten products is iron and is fed directly into an electric arc furnace.
15. The process according to claim 13 wherein the said molten iron can be granulated.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] A detailed description of the invention is hereafter described with specific reference being made to the drawings in which:
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DETAILED DESCRIPTION OF THE INVENTION
[0054] The In-Flight reactor relies on conventional burner design.
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[0056] The nozzle 30 can be a single large diameter nozzle or an assembly of several small diameter orifices as shown in
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[0058] If the process is operated at lower temperatures to produce a solid metallic iron product the solids are removed by high temperature gas filtration, by any other conventional solid/gas separation equipment or by magnetic separation if the solid iron product temperature is below the curie point. The solid iron product is briquetted for transportation to steelmaking facilities. as shown in
[0059] If the process is operated at a higher temperature and the iron product is molten then the molten iron is separated in a high temperature cyclone, or any other high temperature solid/liquid separation equipment and can be collected in a molten bath or fed directly into an electric arc furnace. If a granular product is required for transportation purposes,
[0060] The speed of reaction is a function of particle size and the reduction reactions proceed faster as particle size decreases. Feed solids would be typically less than 3 mm but treatment of coarser feed solids may be practical if the reduction characteristics are favorable. Reaction times are typically of the order of 10 seconds or less.
[0061] An open circuit mass balance is shown in
[0062] Significant improvement in energy efficiency can be achieved by pre-heating the feed materials by heat exchange with the hot reactor products.
[0063] Preheat can be carried out preferably by entraining the iron oxide fines in the feed reduction gas stream and preheating the solids/gas mix. Alternatively, the iron oxide fines and the reducing gas stream may be preheated independently, prior to mixing. The feed oxygen may also be preheated. Some preheat options are shown in
[0064] The hydrogen and oxygen are produced on site in an electrolyzer 70 represented diagrammatically in
[0065] The reaction flame is a hot reducing gas and the iron oxide is rapidly converted into metallic iron in a hot gas stream containing the excess reducing gas and steam.
[0066] If hydrogen is the reducing gas the remaining gas, after removal of the metallic iron, contains only hydrogen and steam. This is fed into a condenser and liquid water is removed for recycling to the electrolyzer. The remaining hydrogen is recycled into the feed hydrogen stream. The hydrogen and oxygen produced by electrolysis are recycled to the IFDR unit. The final products are metallic iron and oxygen.
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[0068] If the IFDR plant is adjacent to a pellet or sinter plant, any excess oxygen can be used to produce enriched air for the pellet or sinter plant furnaces.
[0069] If natural gas is used for the reducing gas the reactor products are metallic iron entrained in a hot gas stream containing carbon monoxide, carbon dioxide, hydrogen and steam plus a small quantity of residual methane. In most cases IFDR plants using natural gas as the reducing gas would be located next to a pellet or sinter plant where fine iron oxide feed materials are readily available. The hot combustible off gas can be used directly as a supplemental fuel for the pellet or sinter plant furnaces as illustrated in
[0070] In the high temperature case, the molten iron can be granulated by any commercial iron granulation process or by the process shown in
[0071] In-Flight Iron (IFI) is produced in a combustion reactor fed by fine iron oxide, a reducing gas and an internal heat generating gas. Typical iron ore fines are predominantly either magnetite (Fe.sub.3O.sub.4) or hematite (Fe.sub.2O.sub.3). Other iron ore mineral fines or fine biomass, or industrial waste products with high enough iron content may be used as feed materials or combined with high-grade ores.
[0072] The combined mixture of gas streams and entrained solids is ignited and forms a reducing flame. Depending on selected operating conditions, the metallic iron product can be either solid or liquid.
[0073] The process can be operated at elevated pressures. However, the design pressure will vary depending on the balance between reduced capital costs and increased operating costs.
[0074] The Following mass balances were obtained using the NASA CEARUN thermodynamic program. The IFDR product composition depends on a) the proportion of excess reducing gas and b) the flow rate of internal heating gas. The mass balances were calculated with the objective of finding product temperatures achieving high recovery of metallic iron while minimizing both excess reducing gas and internal heating gas requirements. Excess Ratio is the ratio of excess reducing gas to gas required for reduction. The basis for all calculations was 1000 Kg metallic iron product.
[0075] If natural gas is used as the reducing gas a hot combustible gas remains after the metallic iron is removed. This can be profitably used as a valuable fuel supplement in adjacent pellet plant or sinter plant furnaces. This approach is expected to be more cost effective than cleaning by conventional methods to yield pure syngas, but could be possible in favorable circumstances.
TABLE-US-00001 Case 1: Iron Oxide: Hematite Flowsheet: Open Circuit Reducing Gas: Methane Excess Ratio: 3.1 Iron Phase: Solid Product Temperature: 781 C. Feed: Fe.sub.2O.sub.3 CH.sub.4 H.sub.2 O.sub.2 Total Kg 1,430 440 80 640 2590 O = 2070 F = 520 O/F = 3.9808 Product: Fe CH.sub.4 H.sub.2 CO CO.sub.2 H.sub.2O Total Kg 1000.4 1.7 129.83 497.02 421.32 539.73 2590 Gas wt % 2.5 8.5 28.4 31.6 29.0
[0076] The hot gas stream contains 36.9% by mass of a hydrogen rich syn-gas with molar H.sub.2/CO ratio of 4.19. The remaining gases are steam, 29.0%, CO.sub.2, 31.6% and methane 2.5%.
TABLE-US-00002 Case 2: Iron Oxide: Magnetite Flowsheet: Open Circuit Reducing Gas: Methane Excess Ratio: 3.0 Iron Phase: Solid Product Temperature: 910 C. Feed: Fe.sub.3O.sub.4 CH.sub.4 H.sub.2 O.sub.2 Total Kg 1,382 382 77.6 620.75 2462.35 O = 2002.75 F = 459.6 O/F = 4.3576 Product: Fe CH.sub.4 H.sub.2 CO CO.sub.2 H.sub.2O Kg 1000.3 0.06 110 462.3 321.2 568.9 2462.46 Gas wt % 0.00 7.5 31.6 22.0 38.9 100
[0077] The hot gas stream contains 39.1% by mass of a hydrogen rich syngas with molar H.sub.2/CO ratio of 3.32. The remaining gases are steam, 38.9%, CO.sub.2, 21.96% and a trace of methane.
TABLE-US-00003 Case 3: Iron Oxide: Magnetite Flowsheet: Closed Circuit Preheat Temperature: 627 C. Reducing Gas: Methane Excess Ratio: 2.5 Iron Phase: Solid Product Temperature: 833 C. Feed: Fe.sub.2O.sub.3 CH.sub.4 H.sub.2 O.sub.2 Total Kg 1383 334 49 394 2160 O = 1777 F = 383 O/F = 4.64 Product: Fe CH.sub.4 H.sub.2 CO CO.sub.2 H.sub.2O Kg 1000 0.4 90.0 400.4 286.1 382.7 2159.6 Gas wt % 0.01 7.76 34.53 24.67 33.0
[0078] The hot gas stream contains 42.29% by mass of a hydrogen rich syngas with molar H.sub.2/CO ratio of 3.15. The remaining gases are 24.67% CO.sub.2 and 33% steam.
TABLE-US-00004 Case 4: FIG. 8 Iron Oxide: Magnetite Flowsheet: Open Circuit Reducing Gas: Hydrogen Excess Ratio: 3.7 Iron Phase: Solid. Product Temperature: 1185 C. Feed: Fe.sub.3O.sub.4 H.sub.2 O.sub.2 Total kg 1382 224 406 2012 O = 1788 F = 224 O/F = 7.9821 Product: Fe H.sub.2 H.sub.2O Total kg 1000 125 887 2012 Gas wt % 12.4 83.6 H.sub.2 used 99 (44.2%)
[0079] The hot gas stream contains 12.4% by mass of hydrogen and 83.6% steam.
TABLE-US-00005 Case 5: FIG. 9 Iron Oxide: Magnetite Flowsheet: Closed Circuit Preheat Temperature: 627 C. Reducing Gas: Hydrogen Excess Ratio: 2.8 Iron Phase: Solid Product Temperature: 833 C. Feed: Fe.sub.3O.sub.4 H.sub.2 O.sub.2 Total kg 1382 182.6 95.5 1660.1 O = 1477.5 F = 182.8 O/F = 8.0915 Product: Fe H.sub.2 H.sub.2O Total kg 1000 122.4 538.1 1660.1 Gas wt % 12.4 83.6 H.sub.2 used 60.2 (33.0%
[0080] Note: The excess hydrogen is directly recycled from the condenser and the hydrogen contained in the water is recovered by electrolysis and recycled. Consequently there is no net consumption of hydrogen and the only off gas is 382 kg of oxygen.
TABLE-US-00006 Case 6: Iron Oxide: Magnetite Flowsheet: Open Circuit Reducing Gas: Hydrogen Excess Ratio: 7.9 Iron Phase: Liquid Product Temperature: 1589 C. Feed: Fe.sub.3O.sub.4 H.sub.2 O.sub.2 Total Kg 1,382 405.9 907.2 2695.1 Product: Fe H.sub.2 H.sub.2O Kg 997.8 243.5 1450 2691.3* Gas wt % 14.38 85.62 100 *2.2% Fe loss to minor iron species.
The hot gas stream contains 18.5% by mass of hydrogen and 81.5% steam. With pre-heating and recycling hydrogen demand is reduced by 18%.
TABLE-US-00007 Case 7: FIG. 11. Off gas to Pellet Plant. Iron Oxide: Magnetite Flowsheet: Closed Circuit Preheat Temperature: 900 C. Reducing Gas: Methane Excess Ratio: 2.1 Iron Phase: Solid Product Temperature: 833 C. Feed: Fe.sub.3O.sub.4 CH.sub.4 H.sub.2 O.sub.2 Total Kg 1383 334 49 394 2160 O = 1777 F = 383 O/F = 4.64 Product: Fe CH.sub.4 H.sub.2 CO CO.sub.2 H.sub.2O Kg 1000 0.4 90.0 400.4 286.1 382.7 2159.6 Gas wt % 0.01 7.76 34.53 24.67 33.0
[0081] The hot gas stream contains 42.29% by mass of a hydrogen rich syngas with molar H.sub.2/CO ratio of 3.15. The remaining gases are 24.67% CO.sub.2 and 33% steam.
Cost Estimates
[0082] With current interest focused on the reduction of atmospheric carbon dioxide and the long-term goal of a hydrogen economy, future costs for hydrogen and electric power are projected to decrease significantly. There is also interesting research into novel power generation technology that could become commercial in the medium term future. One example is the use of nano pulse technology as reported by Dharmaraj and Kumar (IJEE vol 3, 1, 2012 pp 129-136) They report experimental results of 0.58 W for the production of 0.58 ml/s of hydrogen, that is 1 kWh per 3600 L. A more conservative value of 1 kWh for 3000 L is used below.
[0083] The amount of hydrogen required for the production of 1000 kg of metallic iron varies greatly with plant configuration as shown in the following table:
TABLE-US-00008 Flowsheet Kg H.sub.2 Kg CH.sub.4 Case 4 FIG. 8 224 0 Case 5 FIG. 9 182* 0 Case 7 FIG. 11 49 334 * Recycled so no net demand.
[0084] In the case of hydrogen as the reducing gas, the products are metallic iron and oxygen only. If the IFDR plant is adjacent to a pellet plant or sinter plant, the oxygen can be used to enrich the combustion air. However, without corresponding cost benefit data, the following cost estimates do not include any oxygen credits. A recent NEL estimate of the cost of hydrogen produced by electrolysis and wind power in Minnesota gave figures in the range $3.15 to $3.25 per kg of hydrogen. An average of $3.20/kg is used in the following IFDR estimates:
TABLE-US-00009 Case 5: Hydrogen. Closed circuit with pre-heat No credit for excess oxygen Units Cost $ Total $ Taconite Concentrate Metric tons 1.5 45.00 67.50 Water 750 gal 0.3 2.00 0.60 Hydrogen by electrolysis Kg 60 3.20 192.0 Labor Man Hours 0.5 35.00 17.50 Maintenance & Other $/t 15 1.00 15.00 Briquetting $/t 1 10.00 10.00 Total Cost 302.6 Iron Concentration 97%
TABLE-US-00010 Case 7: Natural gas and off-gas going to pellet plant Units Cost $ Total $ Taconite Concentrate Metric tons 1.5 45.00 67.50 Water 750 gal 0.3 2.00 0.60 Natural Gas Kg 334 0.20 66.80 Hydrogen Kg 49 3.20 156.80 Labor Man Hours 0.5 35.00 17.50 Maintenance & Other $/t 15 1.00 15.00 Briquetting $/t 1 10.00 10.00 Total Cost 334.2 Iron Concentration 97%
[0085] Future Projection:
[0086] With a nano pulse power supply for electrolysis Case 5 hydrogen requirements are 60 kg or 672,000 L=224 kWhr
[0087] At $0.07/kWh the cost for power is $47.73 per metric ton of iron.
TABLE-US-00011 Units Cost $ Total $ Taconite Concentrate Metric tons 1.5 45.00 67.50 Water 750 gal 0.3 2.00 0.60 Electricity kWh 224 0.07 15.68 Labor Man Hours 0.5 35.00 17.50 Maintenance & Other $/t 15 1.00 15.00 Briquetting $/t 1 10.00 10.00 Total Cost 126.28 Iron Concentration 97%
UBS estimates for Shaft Furnace DRI and Mesabi Nuggets are given below for comparison. Case 5 and case 7 above are comparable Whereas the future estimate indicates the substantial cost benefits achievable with low electrolysis costs.
TABLE-US-00012 Units Cost $ DRI Shaft Cost Assumptions Source: Energiron, Midrex, UBS estimates Iron Ore Tons 1.45 170 $246.5 Natural Gas mmbtu 8.9 3.75 $33.5 Electricity kwh 95 0.07 $6.7 Labor Man Hours 0.14 $35 $4.9 Maintenance and Other $/t 15 $1 $15.0 Total Cost $306.5 Iron Concentration 92.0% Assuming ore cost is $ the same adjusted cost is DRI Rotary Hearth Furnace Cost Assumptions Source: Midrex, UBS estimates Iron Ore Tons 1.6 155.0 $248.0 Thermal Coal Tons 0.5 65 32.5 Natural Gas mmbtu 4.4 3.75 16.3 Electricity kwh 200 0.07 14.0 Labor Man Hours 0.2 35 7.0 Maintenance and Other $/t 30 1 30.0 Total Cost $347.8 Iron Concentration 96.5% Note: See NUCOR estimate below for DRI costs of $369.
Molten Iron
[0088] For the production of 1000 kg of molten iron from magnetite using a nano pulse power supply for electrolysis 3,482,000 L of hydrogen is required. The power needed is 3,482,000/3000=1.160 kWh. At $0.07/kWh the cost for power is $81.26 per metric ton of iron.
TABLE-US-00013 Units Cost $ Total $ Taconite Concentrate Metric tons 1.5 45.00 67.50 Water 750 gal 0.7 2.00 1.40 Electricity kWh 821 0.07 57.47 Labor Man Hours 0.5 35.00 17.50 Maintenance & Other $/t 15 1.00 15.00 Briquetting $/t 1 10.00 10.00 Total Cost. 168.87 Iron Concentration 99% Note: See NUCOR estimate below for Adjusted pig iron cost of $436
TABLE-US-00014 DRI and PIG IRON COSTS (extract from NUCOR PRESENTATION March 2014) DRI VERSUS PIG IRON COST COMPARISON (using estimated long-term prices) $/ton Iron Ore (62% FE, FOB Brazil) $125 $125 Pellet Premium $40 $40 Iron Premium (BF = 65% Fe & DRI = 68% Fe) $7 $13 Freight $25 $15 Iron Ore Consumption (BF = 1.6 ton & DRI = 1.5 ton) $315 $290 Cash Conversion Costs $70 $35 BF Reductant (100% coke) $107 DRI Reduction (11 mmbtus @$4) $44 Iron Unit Cost $492 $369 BF with sinter plant cost savings $30 BF Cost Savings by Substituting 40% coke Usage with PCI & natural gas $11 BF Higher Value-In-Use Benefit $15 Adjusted BF Iron Unit Cost $436
[0089] An improved embodiment of the invention is described in connection with
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TABLE-US-00015 Mesabi Slag Concentrate % Cement % SiO.sub.2 1.87 77.9 33 CaO 0.27 11.3 45 Al.sub.2O.sub.3 0.13 5.4 11 MgO 0.13 5.4 11 2.40 100.0 100
[0097] While this invention may be embodied in many different forms, there are shown in the drawings and described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated.
[0098] This completes the description of the preferred and alternate embodiments of the invention. Those skilled in the art may recognize other equivalents to the specific embodiment described herein which equivalents are intended to be encompassed by the claims attached hereto.