US20090095132A1 - Processing of metal chloride solutions and method and apparatus for producing direct reduced iron - Google Patents
Processing of metal chloride solutions and method and apparatus for producing direct reduced iron Download PDFInfo
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- US20090095132A1 US20090095132A1 US11/917,287 US91728706A US2009095132A1 US 20090095132 A1 US20090095132 A1 US 20090095132A1 US 91728706 A US91728706 A US 91728706A US 2009095132 A1 US2009095132 A1 US 2009095132A1
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- oxide
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910001510 metal chloride Inorganic materials 0.000 title claims description 30
- 239000002253 acid Substances 0.000 claims abstract description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000008188 pellet Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021553 Vanadium(V) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910001773 titanium mineral Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/18—Reducing step-by-step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/04—Ferrous oxide [FeO]
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
- C21B13/146—Multi-step reduction without melting
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
- C22B5/14—Dry methods smelting of sulfides or formation of mattes by gases fluidised material
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method and apparatus for processing metal chloride liquors, such as spent acid liquors from either acid leaching of metalliferous minerals or acid pickling of metals, and to a method and apparatus for production of direct reduced iron (DRI).
- metal chloride liquors such as spent acid liquors from either acid leaching of metalliferous minerals or acid pickling of metals
- DI direct reduced iron
- Such metal chloride liquors include:
- Elemental oxide constituents of the ilmenite (other than iron) which are soluble in hydrochloric acid are similarly dissolved to form their respective chlorides.
- the resultant solution from this type of reaction would typically have a composition similar to the example given in the table below:
- This acid regeneration is commonly done by pyrohydrolysis, in which the metal chloride reacts with water and oxygen to recover the acid, producing a metal oxide as a by-product.
- Pyrohydrolysis is conducted at temperatures which may range from 600° C. to 1200° C. but preferably in the range of 850° C. to 950° C.
- the fluidising gas is typically air.
- Sufficient fuel is added to maintain reaction temperature and to control oxygen potential.
- the off-gas, containing products of combustion and hydrochloric acid vapour, is treated for recovery of the hydrochloric acid component.
- Pyrohydrolysis may be carried out by one of two well-known methods utilised in the current art, namely:
- the metal chloride liquor is first evaporated to a dry pelleted form before feeding to a pyrohydrolysis reactor of the fluid bed type.
- the evaporator in this instance may preferably be of the fluid bed type or alternatively rotary equipment may be used, according to normal practice for the thermal evaporation of water from salts in solution.
- WO93/16000 is particularly advantageous for acid regeneration in acid leaching processes as it results in a highly concentrated, superazeotropic, acid solution for return to the leaching step.
- the present invention aims to provide a process of improved commercial viability, and apparatus for conducting the process.
- the invention provides a process for regeneration of acid and metal from spent acid liquor containing metal chloride in aqueous solution, including the steps of, in sequence:
- the metal is iron or is predominantly iron.
- the reduction step is conducted as a two stage reduction reaction, including a first stage reduction reaction to a lower oxidation state oxide, using a partially combusted fuel as a reducing agent, and a second stage reduction reaction in which the lower oxidation state oxide is converted to the metal.
- the first reduction stage is conducted in a first fluid bed reduction reactor in which the metal oxide is contacted with the fuel and a sub-stoichiometric amount of oxygen.
- the fuel and oxygen may be contacted prior to the first reduction stage.
- the off-gas of the first reduction stage is used as the reducing agent for the second reduction for the second stage.
- the off-gas from the second stage reduction reactor is oxidized to provide energy for the concentration or pyrohydrolysis steps of the process.
- the hot gas required for the evaporation of the metal chloride liquor is provided by the off-gases from the oxide pellet metallising stage.
- the invention provides a process for treatment of a metal oxide feed, including the steps of:
- the first and second stages reduction reactions are carried out in respective first and second fluid bed reduction reaction chambers.
- the metal oxide feed is formed by pyrohydrolysis of a spent acid liquor containing a metal halide, preferably chloride.
- FIG. 1 is a flowchart of processing of a spent metal chloride liquor in accordance with a first embodiment of the invention
- FIG. 2 is a flowchart of processing of a spent metal chloride liquor in accordance with a second embodiment of the invention
- FIG. 3 is a flowchart of processing of a spent metal chloride liquor in accordance with a third embodiment of the invention.
- FIG. 4 is a flowchart of processing of an iron ore to iron metal.
- FIG. 1 illustrates a first embodiment of the invention, which includes evaporation and pelletisation of the metal chloride (MeCl) liquor prior to pyrohydrolysis.
- MeCl metal chloride
- Spent leach liquor derived from the leaching of iron or other metallic oxide or spent pickle liquor derived from a steel or metal finishing process is injected into an evaporator 110 of a fluid bed, rotary kiln or other suitable type.
- the iron or metal chloride product discharged from the evaporator is preferentially a pelleted solid.
- the hot gas providing the heat source for this evaporation is derived from the off-gas of the two metallising stages hereinafter described, further oxidised in an afterburner section 112 of the evaporator.
- the evaporator product is fed to a pyrohydrolysis reactor 114 , normally of the fluid bed type, where the iron or other metal chlorides are converted to metallic oxides by reaction with water at a temperature preferably in the range of 600° C. to 1200° C.
- the water for this reaction may be provided by combustion of the fuel used and by residual water of crystallisation in the reactor feed from the evaporator.
- spent liquor or concentrated spent liquor may be substituted for part or all of the pelletised material fed to the pyrohydrolysis reactor.
- Metal oxide pellets are discharged at a high temperature from the pyrohydrolysis reactor into the a fluid bed gasifying reactor (gasifier) 116 , which serves as the first stage reduction reactor, operating at approximately 1000° C. ⁇ 100° C.
- the gasifier may be supplied with either a solid, liquid or gaseous hydrocarbon fuel such as is appropriate to local availability and cost structures. Suitable fuels may include coal, oil, or natural gas.
- the fuel is converted to a reducing gas predominantly consisting of hydrogen and carbon monoxide.
- the feed to the first stage reduction unit may be augmented or (as discussed later with reference to FIG. 4 ) entirely replaced by iron ore or metallic oxide wastes such as mill scales and baghouse dusts.
- metallic oxide wastes may mixed with the metal chloride liquor before the evaporation step.
- the oxygen for these reactions may be supplied either as ambient or preheated air and with or without oxygen enrichment.
- the aim is to ensure that only sufficient oxygen is used to provide enough heat of combustion to maintain the endothermic reactions that generate the CO and H 2 components necessary for the metal oxide reduction reactions occurring simultaneously. For example, it has been found that satisfactory results may be obtained with an oxygen supply of between 30% to 50% of the full stoichiometric combustion requirement.
- the bed of FeO acts as a catalyst for the gasification reactions.
- the metal oxide is converted rapidly, in the case of iron (III) oxide, into an oxide of lower valence, Fe(II), without metallising. It is important that the reduction takes place rapidly so that the formation of FeO is predominant and the formation of the intermediate oxide Fe 3 O 4 is minimised, as too high a proportion of Fe 3 O 4 may lead to incipient fusion taking place and the resultant ‘stickiness’ leading to de-fluidisation of the bed.
- partially reduced solid oxide pellets are elevated by means of a pneumatic “J-valve” fluid power or other suitable device into the metallising fluid bed reactor train 118 .
- the gases exiting the first stage reactor are used as the fluidising medium in the second stage or metallising reactor and contain sufficient residual reducing gases H 2 and CO for the required reaction.
- char may be formed in the first stage and is carried with the oxide pellets into the second stage.
- the temperature of the second reactor chamber is slightly lower than in the first reactor—for example about 900° C. ⁇ 100° C.—and the residence time in this reactor is of the order of one hour for maximum conversion of oxide to metal.
- the reactions in the second stage reduction are:
- the product from the metallising stage is indirectly cooled under such conditions as to exclude air and so avoid any reoxidation of the product which could occur whilst the material is at an elevated temperature. Nominally, the metallised pellets must be cooled to less than 200° C. or lower before contact with air is allowed.
- the indirect solids cooler 20 may be of any suitable type, as known in the art. Where air is used as an indirect cooling medium, as it is in the illustrated cooler, the resultant hot air may be used as the air feed to the gasifier 116 .
- the hot gas required for the evaporation of the metal chloride liquor is provided by the off-gases from the oxide pellet metallising stage.
- the gases are first passed through the afterburner 112 where any excess carbon monoxide and hydrogen are converted to extra heat for use in the evaporator.
- heat may be recovered from the hot metal pellets for use in preheating the air feed to the first stage reduction reactor or elsewhere in the plant.
- the metallisation step adds less than 20%, and most likely only about 10%, to the total fuel requirements of the process, compared to the process of WO93/16000, but with a substantial increase in the economic value of the end products.
- the above process provides a single solution to the steel industry for processing of pickle liquor and recycling of iron oxide wastes such as mill scale and baghouse dust, producing regenerated acid and direct reduced iron as valuable products.
- Higher zinc baghouse dusts may be added to the spent liquor stream for processing and bound in the inert iron oxide pellets produced by the pyrohydrolysis step for disposal without metallisation.
- the acid regeneration plant also has the capability to handle waste water streams generated during normal steelmaking operations or from site storm water run-off.
- This water may contain fine oxides, oil (from rolling mills), fine coal/carbon or chlorides and would be fed into the evaporator or used for acid absorption, depending on the contaminants present.
- the process produces no solid or liquid effluents, and dioxins and furans have been below the level of detection during test operations.
- Pyrohydrolysis was conducted at a nominal temperature of between 850° C. to 950° C.
- Iron oxide pellets from pyrohydrolysis were first reduced to the monovalent state and then fully reduced to the metallised state.
- the relevant data are given in Table 2 below.
- the temperature in the first stage was 950° C. and the retention time was half an hour.
- the temperature in the second stage was 930° C. and the retention time was two and a half hours.
- the iron product from this trial was non-pyrophoric; therefore no briquetting or special handling would be required for subsequent safe use.
- This embodiment of the invention operates at essentially atmospheric or low pressure and none of the major process vessels or equipment need be certified according Australian Standard AS 1210-1997 and any amendments thereof.
- FIG. 2 illustrates a second embodiment of the invention, in which the spent metal chloride liquor is fed directly to the pyrohydrolysis reactor 214 without prior evaporation and pelletisation.
- the illustrated process are constructed and operated in similar manner to their analogously numbered components described above with reference to FIG. 1 , except that the pyrohydrolysis reactor typically will need to be larger due to the more dilute metal chloride feed liquor.
- the off-gases from the stage 2 reduction are fed to an afterburner 212 and waste heat recovery unit 213 and the waste heat is recovered for use elsewhere in the plant.
- the off-gases from the stage 2 reduction 318 are fed directly to the pyrohydrolysis unit 314 for further combustion and recovery of heat values.
- FIGS. 2 , 3 and 4 the reference numerals are allocated by analogy to those of FIG. 1 , with ‘200-series’ numerals used in FIG. 2 , ‘300-series’ numerals used in FIG. 3 and ‘400-series’ numerals used in FIG. 4 .
- FIG. 4 illustrates an alternative embodiment, in which iron ore fines or iron oxide wastes are reduced to iron.
- the iron ore or oxide fines are fed to a fluid bed preheater 422 , using the residual chemical and thermal energy in the off-gases from the second stage reduction reactor 418 .
- the off-gases which contain CO and H 2 , are fed to an afterburner 424 in the base of the preheater 422 and the combustion gases fed to the fluid bed.
- the preheated feed is then fed to the two-stage co-current reduction reactor 416 , 418 , which operates as described above with reference to FIGS. 1 to 3 .
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Abstract
A process and apparatus for regeneration of acid and metal from spent acid liquors includes the steps of, optionally, concentrating (110) the liquor to a concentrated liquor or solid, pyrohydrolysing (114) to regenerate the acid and form metal oxide pellets, and reducing the oxide to metal in a two stage reduction reactor (116, 118) using a partially combusted fuel as reducing agent. Also disclosed is a two-stage reduction process and reactor for production of direct reduced iron (DRI) from iron oxide ores or wastes, including a first stage (416) in which the oxide feed is contacted with a fuel and a sub-stoichiometric amount of an oxygen source to produce a lower oxidation state oxide, and a second stage (418) in which the lower oxidation stage oxide is contacted with off-gases from the first stage to produce iron metal.
Description
- 1. Field of the Invention
- The present invention relates to a method and apparatus for processing metal chloride liquors, such as spent acid liquors from either acid leaching of metalliferous minerals or acid pickling of metals, and to a method and apparatus for production of direct reduced iron (DRI).
- 2. Description of Related Art
- There are several important industrial processes which produce as a by-product metal chloride liquors, in the form of spent acid liquors which contain metal chloride in solution.
- Such metal chloride liquors include:
-
- Spent leach liquors resulting from the acidic digestion of a mineral species such as, but not necessarily restricted to, the mineral known as ilmenite. The acid in this case may be, but is not necessarily restricted to, hydrochloric acid.
- So-called ‘pickle liquor’ resulting from an acid treatment or pickling, or etching of metallic surfaces for cleaning of rust or oxide scale. The acid in this case may be, but is not necessarily restricted to, hydrochloric acid.
- In the first of these cases, ilmenite, a titanium mineral, is leached in hydrochloric acid to yield a synthetic rutile and spent leach liquor containing iron and other chlorides in solution, together with a small excess of hydrochloric acid, according to the generalised reaction equation given below:
-
FeO.TiO2+2HCl→FeCl2+TiO2+H2O - Elemental oxide constituents of the ilmenite (other than iron) which are soluble in hydrochloric acid are similarly dissolved to form their respective chlorides. The resultant solution from this type of reaction would typically have a composition similar to the example given in the table below:
-
TABLE 1 Typical analysis of spent metal chloride liquor from acid leaching of ilmenite. Compound Mass % grams/litre TiCl4 0.08 1.14 FeCl2 27.37 368.59 CrCl3 0.03 0.44 MgCl2 0.56 7.55 CaCl2 0.26 3.56 MnCl2 0.29 3.90 SiCl4 0.02 0.21 VCl5 0.11 1.52 AlCl3 0.56 7.57 HCl 3.71 50.00 H2O 67.00 902.46 - In the second case, steel products that have acquired an oxide or rust coating are often subjected to a process referred to as ‘pickling’ wherein the oxide or rust coating is removed by passing the steel through a hot solution of hydrochloric or other acid. In the case of the use of hydrochloric acid, the reactions involved may be simplified to the following:
-
Fe2O3+Fe+6HCl→3FeCl2+3H2O - Known processes for treatment of such metal chloride liquors concentrate on regeneration and recovery of the acid, for recycling to the acid leaching or pickling process.
- This acid regeneration is commonly done by pyrohydrolysis, in which the metal chloride reacts with water and oxygen to recover the acid, producing a metal oxide as a by-product.
- In the case of iron chloride, the predominant reactions taking place during pyrohydrolysis may be expressed as follows:
-
2FeCl2+2H2O+ 1/2O2→Fe2O3+4HCl - Pyrohydrolysis is conducted at temperatures which may range from 600° C. to 1200° C. but preferably in the range of 850° C. to 950° C. The fluidising gas is typically air. Sufficient fuel is added to maintain reaction temperature and to control oxygen potential. The off-gas, containing products of combustion and hydrochloric acid vapour, is treated for recovery of the hydrochloric acid component.
- Pyrohydrolysis may be carried out by one of two well-known methods utilised in the current art, namely:
-
- In a spray tower, wherein the liquor is sprayed into a void chamber and reacted with hot gases derived from the burning of a liquid or gaseous fuel. In this instance the metal oxide product is in the form of a fine powder.
- In a fluidised bed reactor, wherein the liquor is injected into a fluidised bed of previously manufactured metal oxide, and the mass maintained at high temperature by the injection of a gaseous, liquid or solid fuel or any mixture thereof. In this type of equipment, the metal oxide residue may be in the form of small pellets with a nominal size of 1 mm to 2 mm in diameter.
- As a further development, as instanced in International Patent Application PCT/AU93/00056 (WO93/16000), the metal chloride liquor is first evaporated to a dry pelleted form before feeding to a pyrohydrolysis reactor of the fluid bed type. The evaporator in this instance may preferably be of the fluid bed type or alternatively rotary equipment may be used, according to normal practice for the thermal evaporation of water from salts in solution.
- The process of WO93/16000 is particularly advantageous for acid regeneration in acid leaching processes as it results in a highly concentrated, superazeotropic, acid solution for return to the leaching step.
- The contents of WO93/16000 are incorporated herein by reference.
- Other known acid regeneration processes include the KeramChemie process, in which the metal chloride liquor undergoes pyrohydrolysis without pre-concentration, resulting in a sub-azeotropic acid solution.
- The present invention aims to provide a process of improved commercial viability, and apparatus for conducting the process.
- In one form, the invention provides a process for regeneration of acid and metal from spent acid liquor containing metal chloride in aqueous solution, including the steps of, in sequence:
-
- Optionally, concentrating the liquor to form a liquor concentrate or solidifying the liquor concentrate to form a solid metal chloride;
- Pyrohydrolysing the liquor, concentrated liquor or solid metal chloride in a reactor to regenerate the acid and form a metal oxide; and
- Reducing the metal oxide to metal.
- Preferably, the metal is iron or is predominantly iron.
- In one preferred form, the reduction step is conducted as a two stage reduction reaction, including a first stage reduction reaction to a lower oxidation state oxide, using a partially combusted fuel as a reducing agent, and a second stage reduction reaction in which the lower oxidation state oxide is converted to the metal.
- Preferably, the first reduction stage is conducted in a first fluid bed reduction reactor in which the metal oxide is contacted with the fuel and a sub-stoichiometric amount of oxygen.
- Alternatively, the fuel and oxygen may be contacted prior to the first reduction stage.
- Preferably also, the off-gas of the first reduction stage is used as the reducing agent for the second reduction for the second stage.
- In a further preferred form, the off-gas from the second stage reduction reactor is oxidized to provide energy for the concentration or pyrohydrolysis steps of the process. Preferably the hot gas required for the evaporation of the metal chloride liquor is provided by the off-gases from the oxide pellet metallising stage.
- In a further form, the invention provides a process for treatment of a metal oxide feed, including the steps of:
-
- Contacting the metal oxide feed with a reducing agent comprising a fuel and a sub-stoichiometric amount of oxygen, in a first stage reduction to form a lower oxidation state oxide; and
- Feeding the lower oxidation state oxide formed by the first stage reduction and off-gases from the first stage to a second reduction stage wherein the lower oxidation state oxide is reduced to the metal.
- Preferably, the first and second stages reduction reactions are carried out in respective first and second fluid bed reduction reaction chambers.
- Preferably, the metal oxide feed is formed by pyrohydrolysis of a spent acid liquor containing a metal halide, preferably chloride.
- Further aspects of the invention are as set out in the claims.
- Further preferred embodiments of the invention will now be described with reference to the accompanying drawings, in which:
-
FIG. 1 is a flowchart of processing of a spent metal chloride liquor in accordance with a first embodiment of the invention; -
FIG. 2 is a flowchart of processing of a spent metal chloride liquor in accordance with a second embodiment of the invention; -
FIG. 3 is a flowchart of processing of a spent metal chloride liquor in accordance with a third embodiment of the invention, and -
FIG. 4 is a flowchart of processing of an iron ore to iron metal. -
FIG. 1 illustrates a first embodiment of the invention, which includes evaporation and pelletisation of the metal chloride (MeCl) liquor prior to pyrohydrolysis. - Spent leach liquor derived from the leaching of iron or other metallic oxide or spent pickle liquor derived from a steel or metal finishing process is injected into an
evaporator 110 of a fluid bed, rotary kiln or other suitable type. The iron or metal chloride product discharged from the evaporator is preferentially a pelleted solid. The hot gas providing the heat source for this evaporation is derived from the off-gas of the two metallising stages hereinafter described, further oxidised in anafterburner section 112 of the evaporator. - The evaporator product is fed to a
pyrohydrolysis reactor 114, normally of the fluid bed type, where the iron or other metal chlorides are converted to metallic oxides by reaction with water at a temperature preferably in the range of 600° C. to 1200° C. The water for this reaction may be provided by combustion of the fuel used and by residual water of crystallisation in the reactor feed from the evaporator. - The concentration, pelletisation and pyrohydrolysis steps and their equipment and operating parameters are known per se, and are described in more detail in WO93/16000.
- It should be noted that spent liquor or concentrated spent liquor may be substituted for part or all of the pelletised material fed to the pyrohydrolysis reactor.
- Metal oxide pellets are discharged at a high temperature from the pyrohydrolysis reactor into the a fluid bed gasifying reactor (gasifier) 116, which serves as the first stage reduction reactor, operating at approximately 1000° C.±100° C. The gasifier may be supplied with either a solid, liquid or gaseous hydrocarbon fuel such as is appropriate to local availability and cost structures. Suitable fuels may include coal, oil, or natural gas.
- In the gasifier, the fuel is converted to a reducing gas predominantly consisting of hydrogen and carbon monoxide.
- As a further embodiment, the feed to the first stage reduction unit may be augmented or (as discussed later with reference to
FIG. 4 ) entirely replaced by iron ore or metallic oxide wastes such as mill scales and baghouse dusts. Alternatively, or in addition, metallic oxide wastes may mixed with the metal chloride liquor before the evaporation step. - The gasifying reactions involved are quite complex but have been exhaustively studied and reported in the literature. Examples of some of the more simple reactions involved are given below:
-
C+O2→CO2 -
2C+O2→2CO -
2C+1½O2→CO+CO2 -
2C+3H2O→CO+CO2+3H2 -
CH4+2O2→CO2+2H2O -
CH4+H2O→CO+3H2 - The oxygen for these reactions may be supplied either as ambient or preheated air and with or without oxygen enrichment. The aim is to ensure that only sufficient oxygen is used to provide enough heat of combustion to maintain the endothermic reactions that generate the CO and H2 components necessary for the metal oxide reduction reactions occurring simultaneously. For example, it has been found that satisfactory results may be obtained with an oxygen supply of between 30% to 50% of the full stoichiometric combustion requirement.
- The bed of FeO acts as a catalyst for the gasification reactions.
- In the gasifier, the metal oxide is converted rapidly, in the case of iron (III) oxide, into an oxide of lower valence, Fe(II), without metallising. It is important that the reduction takes place rapidly so that the formation of FeO is predominant and the formation of the intermediate oxide Fe3O4 is minimised, as too high a proportion of Fe3O4 may lead to incipient fusion taking place and the resultant ‘stickiness’ leading to de-fluidisation of the bed.
- The reactions taking place in the first stage reduction are:
-
3Fe2O3+H2→2Fe3O4+H2O -
3Fe2O3+CO→2Fe3O4+CO2 -
Fe3O4+H2→3FeO+H2O -
Fe3O4+CO→3FeO+CO2 - From the gasifier, partially reduced solid oxide pellets—predominantly FeO—are elevated by means of a pneumatic “J-valve” fluid power or other suitable device into the metallising fluid
bed reactor train 118. The gases exiting the first stage reactor are used as the fluidising medium in the second stage or metallising reactor and contain sufficient residual reducing gases H2 and CO for the required reaction. Where coal is used as the fuel for the first reduction stage, char may be formed in the first stage and is carried with the oxide pellets into the second stage. The temperature of the second reactor chamber is slightly lower than in the first reactor—for example about 900° C.±100° C.—and the residence time in this reactor is of the order of one hour for maximum conversion of oxide to metal. - The reactions in the second stage reduction are:
-
FeO+CO→Fe+CO2 -
FeO+H2→Fe+H2O - By using the off-gases from the first stage for the second stage reduction, the minor proportion of Fe3O4 in the reaction products from the first stage is reduced by reaction with the CO.
-
Fe3O4+CO→3FeO+CO2 -
FeO+CO→Fe+CO2 - The product from the metallising stage is indirectly cooled under such conditions as to exclude air and so avoid any reoxidation of the product which could occur whilst the material is at an elevated temperature. Nominally, the metallised pellets must be cooled to less than 200° C. or lower before contact with air is allowed.
- The indirect solids cooler 20 may be of any suitable type, as known in the art. Where air is used as an indirect cooling medium, as it is in the illustrated cooler, the resultant hot air may be used as the air feed to the
gasifier 116. - As mentioned above, the hot gas required for the evaporation of the metal chloride liquor is provided by the off-gases from the oxide pellet metallising stage. The gases are first passed through the
afterburner 112 where any excess carbon monoxide and hydrogen are converted to extra heat for use in the evaporator. Furthermore, heat may be recovered from the hot metal pellets for use in preheating the air feed to the first stage reduction reactor or elsewhere in the plant. - As a result, it is expected that the metallisation step adds less than 20%, and most likely only about 10%, to the total fuel requirements of the process, compared to the process of WO93/16000, but with a substantial increase in the economic value of the end products.
- Furthermore, the above process provides a single solution to the steel industry for processing of pickle liquor and recycling of iron oxide wastes such as mill scale and baghouse dust, producing regenerated acid and direct reduced iron as valuable products. Higher zinc baghouse dusts may be added to the spent liquor stream for processing and bound in the inert iron oxide pellets produced by the pyrohydrolysis step for disposal without metallisation.
- The acid regeneration plant also has the capability to handle waste water streams generated during normal steelmaking operations or from site storm water run-off. This water may contain fine oxides, oil (from rolling mills), fine coal/carbon or chlorides and would be fed into the evaporator or used for acid absorption, depending on the contaminants present.
- The process produces no solid or liquid effluents, and dioxins and furans have been below the level of detection during test operations.
- Operating Data
- During a bench-scale trial with spent liquor derived from the hydrochloric acid leaching of an ilmenite, the following data was recorded:
- Liquor Feed to the Evaporator
- The composition of the feed liquor to the evaporator has been quoted in Table 1 above
- Evaporation Stage
- Evaporation and drying of the solid iron chloride was taken to the point where the so-called water of crystallisation corresponded to an empirical formula of FeCl2.1.5H2O, thus providing sufficient water for the pyrohydrolysis reaction
- Pyrohydrolysis
- Pyrohydrolysis was conducted at a nominal temperature of between 850° C. to 950° C.
- Reduction
- Iron oxide pellets from pyrohydrolysis were first reduced to the monovalent state and then fully reduced to the metallised state. The relevant data are given in Table 2 below.
- The temperature in the first stage was 950° C. and the retention time was half an hour.
- The temperature in the second stage was 930° C. and the retention time was two and a half hours.
-
TABLE 2 Reduction Feed and Product analyses Oxide from Metallised Compound Unit Pyrohydrolysis Product TiO2 % mass 0.11 0.16 Fe2O3 ″ Nil {close oversize brace} 95.5 FeO ″ 6.0 Fe ″ Nil 89.7 Cr2O3 ″ 0.06 0.08 MgO ″ 0.84 1.18 CaO ″ 0.02 0.03 MnO ″ 1.64 2.29 SiO2 ″ 0.13 0.18 V2O5 ″ 0.60 0.84 Al2O3 ″ 0.38 0.54 P2O5 ″ 0.004 0.005 Nb2O5 ″ 0.002 0.003 Slag index ratio Not applicable 1.7 Sponge Iron % mass Not applicable 1.6 - The iron product from this trial was non-pyrophoric; therefore no briquetting or special handling would be required for subsequent safe use.
- The chemical composition and physical state were such that it would be considered satisfactory feed for molten metal or steel production, for example as feedstock for an electric arc furnace.
- Operating Pressures
- This embodiment of the invention operates at essentially atmospheric or low pressure and none of the major process vessels or equipment need be certified according Australian Standard AS 1210-1997 and any amendments thereof.
-
FIG. 2 illustrates a second embodiment of the invention, in which the spent metal chloride liquor is fed directly to thepyrohydrolysis reactor 214 without prior evaporation and pelletisation. - In the embodiment of
FIG. 2 , the illustrated process are constructed and operated in similar manner to their analogously numbered components described above with reference toFIG. 1 , except that the pyrohydrolysis reactor typically will need to be larger due to the more dilute metal chloride feed liquor. - In the arrangement of
FIG. 2 , the off-gases from the stage 2 reduction are fed to anafterburner 212 and wasteheat recovery unit 213 and the waste heat is recovered for use elsewhere in the plant. - In the arrangement of
FIG. 3 , the off-gases from the stage 2reduction 318 are fed directly to thepyrohydrolysis unit 314 for further combustion and recovery of heat values. - In
FIGS. 2 , 3 and 4 the reference numerals are allocated by analogy to those ofFIG. 1 , with ‘200-series’ numerals used inFIG. 2 , ‘300-series’ numerals used inFIG. 3 and ‘400-series’ numerals used inFIG. 4 . -
FIG. 4 illustrates an alternative embodiment, in which iron ore fines or iron oxide wastes are reduced to iron. - The iron ore or oxide fines—for example of diameter about 3 mm—are fed to a
fluid bed preheater 422, using the residual chemical and thermal energy in the off-gases from the secondstage reduction reactor 418. The off-gases, which contain CO and H2, are fed to anafterburner 424 in the base of thepreheater 422 and the combustion gases fed to the fluid bed. - The preheated feed is then fed to the two-stage
co-current reduction reactor FIGS. 1 to 3 . - Though the present invention has been described above with respect to a particular embodiment thereof it is to be understood that the invention is not limited thereto but is capable of variation within the knowledge of a person skilled in the art. All changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein.
- In this specification, the word “comprising” is to be understood in its “open” sense, that is, in the sense of “including”, and thus not limited to its “closed” sense, that is the sense of “consisting only of”. A corresponding meaning is to be attributed to the corresponding words “comprise”, “comprised” and “comprises” where they appear.
- It will further be understood that any reference herein to known prior art is not, unless the indicated to the contrary, an admission that such prior art is commonly known by those skilled in the art to which the invention relates.
Claims (18)
1. A process of regeneration of acid and metal from spent acid liquor containing metal chloride in aqueous solution, including the steps of, in sequence:
(a) optionally, concentrating the liquor to form a liquor concentrate or solidifying the liquor concentrate to form a solid metal chloride;
(b) pyrohydrolysing the liquor, concentrated liquor or solid metal chloride in a reactor to regenerate the acid and form a metal oxide; and
(c) reducing the metal oxide to metal.
2. A process according to claim 1 , wherein the metal is iron or is predominantly iron.
3. A process according to claim 1 , wherein the reduction step is conducted as a two stage co-current reduction reaction.
4. A process according to claim 3 , wherein a first stage reduction reaction to a lower oxidation state oxide uses a partially combusted hydrocarbon fuel as a reducing agent.
5. A process according to claim 4 , wherein the first reduction stage is conducted in a first fluid bed reduction reactor in which the metal oxide is contacted with the fuel and a sub-stoichiometric amount of oxygen.
6. A process according to claim 4 , wherein said oxygen is provided to said first reduction stage as air.
7. A process according to claim 4 , wherein off-gas of the first reduction stage is used as the reducing agent for the second reduction for the second stage.
8. A process according to claim 3 , wherein off-gas from the second stage reduction reactor is oxidized to provide energy for the concentration or pyrohydrolysis steps of the process.
9. A process according to claim 1 , wherein off-gases from the oxide pellet metallising stage are used for the evaporation of the metal chloride liquor.
10. A process according to claim 2 , further including the step of adding iron oxide to the aqueous solution of metal chloride.
11. A process for treatment of a metal oxide, including the steps of:
(a) contacting the metal oxide feed with a reducing agent comprising a fuel and a sub-stoichiometric amount of an oxygen source, in a first stage reduction to form a lower oxidation state oxide; and
(b) feeding the lower oxidation state oxide formed by the first stage reduction and off-gases from the first stage to a second reduction stage wherein the lower oxidation state oxide is reduced to the metal.
12. A process according to claim 11 , wherein said metal is iron.
13. A process according to claim 12 , wherein lower oxidation state oxide is predominantly FeO.
14. A process according to claim 10 , wherein the first and second stages reduction reactions are carried out in respective first and second fluid bed reduction reaction chambers.
15. A process according to claim 14 , including transporting said lower oxidation state oxide from the first reaction chamber to the second reaction chamber by means of an inert gas stream.
16. A process according to claim 12 , wherein said metal oxide feed is an iron ore.
17. A process according to claim 11 , wherein said metal oxide feed is a pelletised metal oxide formed by pyrohydrolytic regeneration of a spent acid liquor containing a metal halide
18. A process according to claim 12 , wherein said metal halide is iron chloride.
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EP3670454A1 (en) * | 2018-12-21 | 2020-06-24 | Höganäs AB (publ) | Pure iron containing compound |
RU2752352C1 (en) * | 2020-09-16 | 2021-07-26 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method for processing waste of iron chloride solutions |
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IN189041B (en) * | 1992-02-12 | 2002-12-14 | Austpac Gold Nl | |
AT408764B (en) * | 1997-04-11 | 2002-03-25 | Engineering Industrieanlagen P | Process for obtaining or recovering hydrochloric acid from solutions which contain metal chlorides, in particular used pickling acid |
US6224649B1 (en) * | 1998-07-06 | 2001-05-01 | Hylsa, S.A. De C.V. | Method and apparatus for reducing iron-oxides-particles having a broad range of sizes |
US6692719B1 (en) * | 2000-11-08 | 2004-02-17 | Hatch Ltd. | Process for regeneration of acid halide solutions |
-
2006
- 2006-06-15 CN CNA2006800257851A patent/CN101223293A/en active Pending
- 2006-06-15 CA CA 2612158 patent/CA2612158A1/en not_active Abandoned
- 2006-06-15 MX MX2007016009A patent/MX2007016009A/en unknown
- 2006-06-15 EP EP06752609A patent/EP1891246A4/en not_active Withdrawn
- 2006-06-15 WO PCT/AU2006/000832 patent/WO2006133500A1/en active Application Filing
- 2006-06-15 US US11/917,287 patent/US20090095132A1/en not_active Abandoned
- 2006-06-15 EA EA200800052A patent/EA200800052A1/en unknown
- 2006-06-15 JP JP2008516073A patent/JP2008546906A/en not_active Withdrawn
- 2006-06-15 KR KR20077029339A patent/KR20080022550A/en not_active Application Discontinuation
-
2008
- 2008-01-14 ZA ZA200800391A patent/ZA200800391B/en unknown
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US2909424A (en) * | 1957-06-04 | 1959-10-20 | United States Steel Corp | Method and device for transferring fluidized solids |
US3135598A (en) * | 1960-04-27 | 1964-06-02 | Yawata Iron & Steel Co | Rapid direct reduction method of iron oxide |
US3178176A (en) * | 1963-01-21 | 1965-04-13 | Miehle Goss Dexter Inc | Side registering mechanism |
US3637369A (en) * | 1969-01-07 | 1972-01-25 | Exxon Research Engineering Co | Fluidized iron ore reduction process |
US6375915B1 (en) * | 1996-11-15 | 2002-04-23 | Keramchemie Gmbh | Method of regenerating a spent pickling solution |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014125275A1 (en) * | 2013-02-15 | 2014-08-21 | Tioxide Europe Limited | Method for producing titanium oxide and iron oxide |
EP2966035A1 (en) * | 2014-07-08 | 2016-01-13 | Kronos International, Inc. | Method for the recovery of hydrochloric acid from metal chloride solutions with a high iron chloride content |
WO2016005042A1 (en) * | 2014-07-08 | 2016-01-14 | Kronos International, Inc. | Process for recovering hydrochloric acid from metal chloride solutions having a high iron chloride content |
Also Published As
Publication number | Publication date |
---|---|
KR20080022550A (en) | 2008-03-11 |
CN101223293A (en) | 2008-07-16 |
WO2006133500A1 (en) | 2006-12-21 |
MX2007016009A (en) | 2008-04-04 |
CA2612158A1 (en) | 2006-12-21 |
EA200800052A1 (en) | 2008-06-30 |
EP1891246A1 (en) | 2008-02-27 |
ZA200800391B (en) | 2008-12-31 |
JP2008546906A (en) | 2008-12-25 |
EP1891246A4 (en) | 2009-11-04 |
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