WO2013156676A1 - Method for processing slags of non-ferrous metallurgy - Google Patents
Method for processing slags of non-ferrous metallurgy Download PDFInfo
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- WO2013156676A1 WO2013156676A1 PCT/FI2013/050409 FI2013050409W WO2013156676A1 WO 2013156676 A1 WO2013156676 A1 WO 2013156676A1 FI 2013050409 W FI2013050409 W FI 2013050409W WO 2013156676 A1 WO2013156676 A1 WO 2013156676A1
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- WO
- WIPO (PCT)
- Prior art keywords
- slag
- furnace
- reduction
- metal
- reduction furnace
- Prior art date
Links
- 239000002893 slag Substances 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000012545 processing Methods 0.000 title claims abstract description 8
- 238000009856 non-ferrous metallurgy Methods 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 230000009467 reduction Effects 0.000 claims abstract description 54
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 150000002739 metals Chemical class 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000007885 magnetic separation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- -1 copper and nickel Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 238000005188 flotation Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000010310 metallurgical process Methods 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- HCTVWSOKIJULET-LQDWTQKMSA-M phenoxymethylpenicillin potassium Chemical compound [K+].N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)COC1=CC=CC=C1 HCTVWSOKIJULET-LQDWTQKMSA-M 0.000 claims 1
- 238000010079 rubber tapping Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- 230000001627 detrimental effect Effects 0.000 abstract description 6
- 239000004035 construction material Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 38
- 239000011133 lead Substances 0.000 description 16
- 229910052745 lead Inorganic materials 0.000 description 7
- 229910052840 fayalite Inorganic materials 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 235000008504 concentrate Nutrition 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000003340 mental effect Effects 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000012719 wet electrostatic precipitator Substances 0.000 description 2
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 238000010169 landfilling Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NXLOLUFNDSBYTP-UHFFFAOYSA-N retene Chemical compound C1=CC=C2C3=CC=C(C(C)C)C=C3C=CC2=C1C NXLOLUFNDSBYTP-UHFFFAOYSA-N 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
-
- 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
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- 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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
-
- 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
-
- 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 invention relates to a method for pro- cessing slags of non-ferrous metallurgy, containing iron and valuable metals, to produce clean fayalite sand which is free of detrimental substances and valu ⁇ able metals and fit for use as a raw material or con ⁇ struction material.
- Slags of non-ferrous metallurgy are generated as by-product of smelting concentrate or converting matte to separate metal fraction from unwanted frac- tions. Slag is primarily a mixture of metal oxides and silicon oxides, but it can also contain metal sulfides and metals in elemental form.
- slag tapped off from a copper flash smelting furnace may contain, depending on the raw material, for instance, magnetite, fayal ⁇ ite, zinc, copper, lead, arsenic, cadmium, and nickel.
- the slag is cleaned either by reduction in an electric furnace or using slag concentration technology. After this kind of cleaning, the slag still contains, depending on the treatment and the raw mate ⁇ rial, about 0.3 - 1% copper, about 1 - 4% zinc, about 0.1 - 0.4% lead and about 0.1 - 0.2% arsenic.
- Such copper and zinc contents in the slag are economically seen quite a loss.
- the waste slag re- ceived from a slag concentrator is very fine, with a grain size of under 0.125 mm. Therefore, detrimental substances contained in the slag may leach when on a dump, thus generating an environmental threat.
- the aim of the slag cleaning process is to maximize the recovery of valuable metals such as Co, Ni, and Cu in an alloy with the lowest possible iron content.
- the amount of metallic iron produced should be kept to a minimum, as the more iron is pre ⁇ sent in the resulting matte or alloy, the greater the costs of the subsequent hydrometallurgical separation of the valuable metals and the resulting disposal of iron residues.
- the purpose of cleaning copper containing slag in an electric furnace is to reduce oxidized copper to metallic copper and trivalent iron to divalent iron and to settle the metallic copper droplets from the slag, thereby forming a metal layer beneath a slag layer.
- oxygen potential of the slag decreases further, also further reductions take place, such as reduction of divalent iron to metallic iron and reduction of oxidized lead to metallic lead.
- Stirring the material in the electric furnace can be used to intensify the reduction reactions.
- US 8088192 B2 discloses a three-phase process for recovering non-ferrous metals from metallurgical residuals.
- the process comprises: (A) a fusion and re ⁇ duction phase during which a certain quantity of iron is reduced and passes into a copper bath; (B) a set ⁇ tling phase during which metal droplets are allowed to settle from the slag to the copper bath and a part of the slag is removed from the furnace; and (C) an oxi ⁇ dation phase involving oxidation of the iron in the copper bath.
- Certain non-ferrous compounds are volati ⁇ lized during phase A and carried away by fumes.
- Vola ⁇ tile heavy metals in particular zinc and lead, are recovered from the fumes by means of separators.
- the reference also teaches stirring the copper bath by in- jection of inert gas in an alternating current plasma arc furnace treating metallurgical residues.
- the pro ⁇ cess is complicated, takes a lot of time and requires large size of reduction furnace.
- Another way to improve reduction in an elec- trie furnace comprises introducing inert gas through porous plugs mounted on the bottom of the furnace.
- Prior art contains various kinds of substanc ⁇ es that can be used as reducing agents in slag reduc ⁇ tion.
- WO 20060240069 teaches the use of carboniferous polymers as metal oxide reducing agents in ferroalloy produc ⁇ tion
- DE 19541673 Al teaches using ground plastic as a reducing agent in a shaft furnace; in IsasmeltTM reac ⁇ tors, coke may be replaced with plastic.
- the object of the present invention is to eliminate drawbacks of the prior art and to provide an improved method for producing clean slag which is free of valuable metals and detrimental substances and suitable for further use as it is as a raw material and/or building material.
- a further object of the present invention is to minimize any losses of valuable metals and to re ⁇ cute the generation of unusable waste in non-ferrous metallurgical industry.
- the present invention relates to processing of slags of non-ferrous metallurgical industry.
- the slag is reduced in a reduction furnace with the help of reducing agents so far that at least part of the iron in the slag turns metallic and detri ⁇ mental zinc, lead, arsenic and cadmium components va- porize.
- Reduction is enhanced by efficient stirring, which also prevents separation of metal phase from the slag.
- the mixture of metal and slag thus produced is tapped into a ladle and slowly cooled, or alternative- ly, tapped into granulation, whereby the mixture is quickly cooled.
- the slag-metal mixture After cooling the slag-metal mixture is crushed, if necessary, and ground to a sufficiently fine particle size. The slag particles and the metal particles are separated from each other by suitable means. The metallic phase is recycled back into the metallurgical process, whereas the slag phase is ready for further use as a raw material or building material. Exhaust gas released from the reduction furnace, containing vaporized metals, is oxidized to convert the metals to metal oxides, which are then separated by suitable means. The metal oxides thus produced may be delivered to further use as a raw material for in ⁇ stance in zinc industry.
- the slag is re- prised, after an optional first reduction stage, in a reduction furnace so far that at least part of the slag' s magnetite and fayalite is reduced, thus gener ⁇ ating elemental iron.
- some valua ⁇ ble metals of the slag such as copper and nickel, re-za to metal and form inclusions in the slag.
- some other valuable metals of the slag such as arsenic, lead and zinc, vaporize and go over to gas phase.
- reduction is carried out in an electric furnace, which may be either of direct cur ⁇ rent type (DC) or of alternating current type (AC) .
- DC direct cur ⁇ rent type
- AC alternating current type
- suitable reduction furnaces comprise a top sub ⁇ merged lance furnace, a Kaldo furnace, or the settler of a suspension smelting furnace
- the reducing agent used in the reduction furnace may be of a solid type or a gaseous type or a combination of these.
- the reducing agent can be se- lected from a group comprising: coke, pulverized coal, graphite, lignite, charcoal, bio-coke, biomass (e.g. sawdust, peat), natural gas, hydrocarbons (e.g.
- mixing can be intensified by at least one of the following ways: in ⁇ jection feeding of the reducing agent, feeding of the reducing agent through a hollow electrode, use of gas ⁇ eous or gas generating reducing agents, feeding inert gas through porous plugs mounted on the bottom of the furnace, and use of electromagnetic stirring.
- the molten slag-metal mixture may be tapped into ladle and slowly cooled, or tapped into granula ⁇ tion, whereby the cooling is quick. After cooling the slag-metal mixture is crushed, if necessary, and ground. After grinding the slag-metal mixture is subjected to a separation process, which may comprise magnetic separa- tion, gravitational separation, flotation, screening, or a combination of these.
- Vaporized metals are oxidized to metal oxides. Gaseous components produced from the reducing agents in the reduction furnace are after-burned. The metal oxides and other solids thus formed are separated from the ex ⁇ haust gas by means of a scrubber, fabric filters, elec ⁇ trostatic precipitator, wet electrostatic precipitator, or a combination of them. The separated metal containing dust is supplied to further use, for instance to a zinc mill to be used as a raw material.
- the slag cleaning method according to the present invention is economically feasible because it yields better recovery of valuable metals, smaller furnace sizes, shorter retention times and, last but not least, efficient conversion of slag to saleable raw materials.
- FIG. 1 is a flow chart illustrating one pos ⁇ sible slag treatment process in accordance with the present invention.
- FIG. 2 is a flow chart illustrating slag pro ⁇ cessing in connection with direct blister flash smelting .
- FIG. 3 is a flow chart illustrating slag pro- cessing in connection with a process comprising a flash smelter and a flash converter.
- slag reduction should be extend ⁇ ed further than in the methods of prior art, so that iron of the slag is at least partly reduced to ele ⁇ mental metal.
- inclusions of valua- ble metals, such as copper, are formed in the iron droplets. Iron needs to be reduced to such a degree that the metal phase contains enough iron to make the metallic phase magnetic. Preferably, 5-30% of the iron should be reduced to metal to enable magnetic separa- tion of metals from the slag.
- the temperature should be kept high enough, in practice between 1400°C and 1500°C, to maintain the mixture of slag and iron-bearing metal in a molten state and to prevent any build-ups on the furnace walls.
- the reten ⁇ tion time may be as short as 0.5 - 2 hours.
- the contact between the reducing agent and the metal oxides is enhanced by mixing, which also increases collisions between the formed metal droplets. This leads to an increased droplet size, further improving the separation of the metal droplets from the slag in the subsequent magnet ⁇ ic separation.
- the method according to the present in ⁇ vention aims to keep the metal droplets within the molten slag and not to let said droplets settle down to the bottom of the furnace.
- mixing is produced by using hollow electrodes, in which con ⁇ nection an efficient mixing zone is generated under the electrodes and the reducing agent is sucked in the slag. In this method, no separate and time-consuming settling phase is needed, which is why the processing time is shorter than in conventional slag reduction furnaces. The energy consumption is reduced and the size of the reduction furnace may be smaller than in conventional slag reduction furnaces.
- Gases exhausted from the reduction furnace contain both metal vapors originating from the slag and components originating from the reducing agents, such as carbon monoxide, hydrogen, etc.
- the exhaust gas is oxidized and after-burned.
- the exhaust gas may also contain small amounts of chlorine, in which case it may be necessary to arrange a sufficient retention time and temperature for the after-burning step.
- After oxidizing and after-burning the exhaust gas is cleaned. Metal oxides and other solids may be recovered from the gas by scrubbing, using fabric fil ⁇ ters, electrostatic separation, wet electrostatic sep- aration, or a combination of these.
- the dust received from the gas cleaning step may be delivered as a raw material for instance into a zinc production plant.
- the slag-metal mixture generated in the re ⁇ duction furnace is tapped from the furnace and cooled.
- the cooled slag is crushed and ground, advantageously to a grain size of 20 ym - 15 mm.
- Metals and possible sulfides are separated from the slag for instance by magnetic separation and/or gravitational separation and/or flotation and/or screening.
- the clean slag can be used, for instance, in road construction, in other land filling applications, or as a raw material in building materials.
- FIG. 1 shows schematically a flow chart of a process for cleaning flash smelter slag.
- Fine concen- trate 11 is mixed with air, or oxygen, or oxygen- enriched air 12 to form a rapidly reacting suspension in a suspension smelting furnace 10.
- Sulfide compounds of the feed 11 ignite, oxidize and release heat, act ⁇ ing as a fuel for the process so that no external en- ergy is needed for smelting.
- molten droplets separate from the gas stream and settle at the bottom of the furnace 10 as distinct matte and slag layers, based on their specif ⁇ ic densities.
- the molten high-grade matte 13 produced in the flash smelting furnace 10 is fed to a converter 15.
- the converter 15 produces blister metal 16 and a small amount of slag 17 having still a relatively high metal content.
- the converter may be, for instance, a Peirce-Smith converter, a Hoboken converter, or of any other suitable type.
- the slag 14 from the flash smelting furnace 10 and the slag 17 from the converter 15 are fed to a reduction furnace 18, which may be, for instance, an electric arc furnace. In the reduction furnace 18, re- duction of the metals comprised in the slags 14, 17 takes place with the help of reducing agents 19 also added to the furnace 18.
- Copper compounds contained in the slag are reduced to metallic copper and iron com ⁇ pounds contained in the slag are, at least partly, re- prised to metallic iron.
- metals hav ⁇ ing a relatively low boiling temperature such as ar ⁇ senic, lead and zinc, vaporize and go over to gas phase. These vaporized metals are discharged from the reduction furnace 18 together with exhaust gas 20.
- the slag and the iron droplets containing copper inclusions are not allowed to separate from each other in the reduction furnace 18 by settling as usual. Instead, the slag-metal mixture is kept in mo ⁇ tion by efficiently mixing so that the metallic copper remains entrapped in the metal droplets.
- the slag-metal mixture 21 is tapped from the reduction furnace 18 and subjected to cooling (not shown) , crushing 22 and grinding 23 to reduce the particle size of the solidified slag-metal mixture.
- a magnetic metal fraction 26 is separated from the remaining clean slag 25 in a separation step 24, which may comprise suitable separation methods, such as magnetic separation, gravitational separation, flotation, filtering, and any combinations of these.
- the separation step 24 produces clean fayal- ite sand 25, which is essentially free of valuable metals and detrimental substances and which can be used as a raw material in a variety of uses, for in ⁇ stance as a constituent of concrete and cement, or which can be mixed with other materials for making roadways .
- Exhaust gas 20 vented from the reduction fur ⁇ nace 18 is passed to an oxidation step 27, where the vaporized metals are converted to metal oxides and substances originating from the reducing agents are after-burned, if necessary.
- the exhaust gas is passed to a cooling step 28 and to a cleaning step 29.
- the cleaning step 29 may com ⁇ prise, for instance, scrubbers, fabric filter units, electrostatic precipitators, wet electrostatic precip- itators, and any combinations of these.
- the metal oxide containing dust 30 from the gas cleaning step 29 may be delivered for instance to a zinc production plant. Clean gas 31 may be released to the atmosphere.
- FIG. 2 shows an example of the new slag cleaning process utilized in connection with a direct blister smelting process.
- the same features are re ⁇ ferred to with the same reference numbers as in FIG. 1.
- blister copper 35 is produced directly from a concentrate in one step. This method is especially suitable for ore concen ⁇ trates with low iron content. Slag 33 received from the direct blister flash smelter 32 still contains substantial amounts of copper and other valuable met ⁇ als, which is why the slag 33 is first fed to an elec ⁇ tric furnace 34 for further recovery of copper blister 36. After the electric furnace 34, the remaining slag 37 is supplied to a reduction furnace 18, the opera ⁇ tion of which corresponds to that discussed in connec ⁇ tion with FIG. 1.
- FIG. 3 shows an example of a slag cleaning process according to the present invention utilized in connection with a process comprising a flash smelter 10 and a flash converter 15.
- This kind of process can be used especially when the iron content of the ore concentrate is high.
- the major difference between FIG. 1 and FIG. 3 is that the process of FIG. 3 comprises an electric furnace 34 for recovery of copper 36 from the slag 33 received from the flash converter 15 be ⁇ fore the slag is fed to a reduction furnace 18.
- the copper-containing metal fraction 26 received from the separation step 24 is recycled to the flash converter 15.
- the flash converting process in the flash convert ⁇ er 15 is very similar to the flash smelting process in furnace 10.
- the oxidation of matte proceeds under highly oxidizing conditions so that the sulfidic matte converts to metallic copper.
- the slag composition was the following: Fe 42%, Si0 2 28%, Zn 4%, Pb 0.3%, As 0.3%, Ni 0.06%, A1 2 0 3 4%, CaO 2%, Cu 1.5% and MgO 1%.
- Fe 42%, Si0 2 28%, Zn 4%, Pb 0.3%, As 0.3%, Ni 0.06%, A1 2 0 3 4%, CaO 2%, Cu 1.5% and MgO 1% In an X-ray diffracto- metric analysis, fayalite, magnetite and hematite were identified as the main minerals of the slag. 800 g of the slag was reduced in a 600 ml crucible with silicon carbide at 1350°C for an hour.
- the product received comprised a mixture of metal alloy and slag having the following composition: Fe 29%, Si0 2 45%, Zn 0.13%, Pb ⁇ 0.02%, As 0.005%, Ni ⁇ 0.004%, A1 2 0 3 7%, CaO 2.6%, Cu 0.25% and MgO 1.3%.
- the slag comprised metal inclu ⁇ sions, containing both copper and iron.
- the reduced slag was pulverized to a grain size smaller than 1 mm. Magnetic separation was carried out to recover metals. The residual non-magnetic slag fraction was very clean, containing only a few small metal inclusions.
- the slag composition was the following: Fe
- the product received comprised a mixture of metal alloy and slag having the following composition: Fe 32%, Si0 2 36.5%, Zn 0.43%, Pb 0.056%, As ⁇ 0.002%, Ni ⁇ 0.002%, AI 2 O 3 5%, CaO 1%, Cu 0.22% and MgO 11%.
- the slag comprised metal inclusions, containing both cop ⁇ per and iron.
- the slag composition was the following: Fe
- the product received comprised a mixture of metal alloy and slag with the following composition: Fe 34%, Si0 2 36%, Zn 0.66%, Pb 0.08%, As ⁇ 0.004%, Ni ⁇ 0.004%, A1 2 0 3 13%, CaO 1.3%, Cu 0.42% and MgO 1.3%.
- the slag comprised metal inclu ⁇ sions, containing both copper and iron.
- the reduced slag was crushed to a grain size of about 1.2 mm and a coarse metal fraction was sepa ⁇ rated by screening.
- the slag fraction was pulverized with a roll mill and subjected to a three-stage mag- netic separation for the recovery of metal.
- the resid ⁇ ual non-magnetic slag fraction had the following com ⁇ position: Fe 33.9%, Si0 2 36%, Zn 0.59%, Pb 0.08%, As ⁇ 0.004%, Ni ⁇ 0.004%, A1 2 0 3 8.2%, CaO 1.4%, Cu 0.36% and MgO 1%.
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
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- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
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Abstract
Description
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Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
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ES13778649.7T ES2649939T3 (en) | 2012-04-16 | 2013-04-15 | Method for processing slag from non-ferrous metallurgy |
CA 2868052 CA2868052A1 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
BR112014025399-4A BR112014025399B1 (en) | 2012-04-16 | 2013-04-15 | METHOD FOR PROCESSING NON-FERROUS METALURGING SLINGS. |
JP2015506272A JP5873600B2 (en) | 2012-04-16 | 2013-04-15 | Nonferrous metallurgical slag processing method |
EA201491800A EA026836B1 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
EP13778649.7A EP2839045B1 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
PL13778649T PL2839045T3 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
KR1020147031314A KR101629598B1 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
CN201380020198.3A CN104302792B (en) | 2012-04-16 | 2013-04-15 | For the method processing the dregs that non-ferric is smelted |
MX2014012467A MX2014012467A (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy. |
US14/394,697 US9435005B2 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
AP2014008003A AP2014008003A0 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metall urgy |
PH12014502185A PH12014502185A1 (en) | 2012-04-16 | 2014-09-29 | Method for processing slags of non-ferrous metallurgy |
ZA2014/08376A ZA201408376B (en) | 2012-04-16 | 2014-11-13 | Method for processing slags of non-ferrous metallurgy |
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FI20125410A FI124912B (en) | 2012-04-16 | 2012-04-16 | A method for treating metallurgical slags of non-ferrous metals |
FI20125410 | 2012-04-16 |
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PCT/FI2013/050409 WO2013156676A1 (en) | 2012-04-16 | 2013-04-15 | Method for processing slags of non-ferrous metallurgy |
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US (1) | US9435005B2 (en) |
EP (1) | EP2839045B1 (en) |
JP (1) | JP5873600B2 (en) |
KR (1) | KR101629598B1 (en) |
CN (1) | CN104302792B (en) |
AP (1) | AP2014008003A0 (en) |
BR (1) | BR112014025399B1 (en) |
CA (1) | CA2868052A1 (en) |
CL (1) | CL2014002734A1 (en) |
EA (1) | EA026836B1 (en) |
ES (1) | ES2649939T3 (en) |
FI (1) | FI124912B (en) |
MX (1) | MX2014012467A (en) |
PH (1) | PH12014502185A1 (en) |
PL (1) | PL2839045T3 (en) |
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WO2016156394A1 (en) | 2015-04-03 | 2016-10-06 | Metallo Chimique | Improved slag from non-ferrous metal production |
EP3341501A4 (en) * | 2015-08-24 | 2018-07-25 | 5n Plus Inc. | Processes for preparing various metals and derivatives thereof from copper- and sulfur-containing material |
US11606956B2 (en) | 2014-09-16 | 2023-03-21 | Premier Tech Technologies Ltée | 4-chloroindole-3-acetic acid for controlling unwanted plants |
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CN105624423A (en) * | 2014-11-05 | 2016-06-01 | 沈阳有色金属研究院 | Low-temperature lead chloride smelting method employing sawdust as reducing agent |
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- 2013-04-15 BR BR112014025399-4A patent/BR112014025399B1/en active IP Right Grant
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- 2013-04-15 PL PL13778649T patent/PL2839045T3/en unknown
- 2013-04-15 CA CA 2868052 patent/CA2868052A1/en not_active Abandoned
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- 2013-04-15 KR KR1020147031314A patent/KR101629598B1/en active IP Right Grant
- 2013-04-15 ES ES13778649.7T patent/ES2649939T3/en active Active
- 2013-04-15 EP EP13778649.7A patent/EP2839045B1/en active Active
- 2013-04-15 US US14/394,697 patent/US9435005B2/en active Active
- 2013-04-15 WO PCT/FI2013/050409 patent/WO2013156676A1/en active Application Filing
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Cited By (6)
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Also Published As
Publication number | Publication date |
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US20150122082A1 (en) | 2015-05-07 |
BR112014025399A2 (en) | 2018-04-10 |
KR20140144734A (en) | 2014-12-19 |
FI20125410A (en) | 2013-10-17 |
EP2839045A4 (en) | 2016-01-13 |
MX2014012467A (en) | 2015-05-08 |
PH12014502185A1 (en) | 2014-12-10 |
PL2839045T3 (en) | 2018-02-28 |
FI124912B (en) | 2015-03-31 |
JP5873600B2 (en) | 2016-03-01 |
EA201491800A1 (en) | 2015-03-31 |
JP2015519473A (en) | 2015-07-09 |
KR101629598B1 (en) | 2016-06-13 |
CN104302792B (en) | 2016-06-22 |
CN104302792A (en) | 2015-01-21 |
US9435005B2 (en) | 2016-09-06 |
CA2868052A1 (en) | 2013-10-24 |
ZA201408376B (en) | 2015-12-23 |
EP2839045B1 (en) | 2017-09-27 |
CL2014002734A1 (en) | 2015-01-23 |
EA026836B1 (en) | 2017-05-31 |
EP2839045A1 (en) | 2015-02-25 |
ES2649939T3 (en) | 2018-01-16 |
AP2014008003A0 (en) | 2014-10-31 |
BR112014025399B1 (en) | 2019-06-18 |
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