CN116497224A - Comprehensive recovery and harmless treatment device and method for valuable metal elements of copper smelting slag - Google Patents
Comprehensive recovery and harmless treatment device and method for valuable metal elements of copper smelting slag Download PDFInfo
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- CN116497224A CN116497224A CN202310492732.6A CN202310492732A CN116497224A CN 116497224 A CN116497224 A CN 116497224A CN 202310492732 A CN202310492732 A CN 202310492732A CN 116497224 A CN116497224 A CN 116497224A
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- Prior art keywords
- furnace
- slag
- smelting
- smelting furnace
- copper
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- 238000003723 Smelting Methods 0.000 title claims abstract description 467
- 239000002893 slag Substances 0.000 title claims abstract description 411
- 239000010949 copper Substances 0.000 title claims abstract description 276
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 276
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 238000000034 method Methods 0.000 title claims abstract description 97
- 238000011084 recovery Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 276
- 229910052742 iron Inorganic materials 0.000 claims abstract description 133
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 96
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003546 flue gas Substances 0.000 claims abstract description 95
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 79
- 239000011701 zinc Substances 0.000 claims abstract description 79
- 239000011449 brick Substances 0.000 claims description 124
- 239000007788 liquid Substances 0.000 claims description 76
- 230000008569 process Effects 0.000 claims description 66
- 239000007921 spray Substances 0.000 claims description 65
- 238000007599 discharging Methods 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 31
- 239000003245 coal Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 25
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 25
- 238000005485 electric heating Methods 0.000 claims description 22
- 238000007664 blowing Methods 0.000 claims description 21
- 239000010453 quartz Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000004575 stone Substances 0.000 claims description 17
- 229910000805 Pig iron Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003500 flue dust Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000009423 ventilation Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- CVXNLQMWLGJQMZ-UHFFFAOYSA-N arsenic zinc Chemical compound [Zn].[As] CVXNLQMWLGJQMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000571 coke Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000002006 petroleum coke Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- CMFUZVSDFIHEAR-UHFFFAOYSA-N [Fe].[Si].[Ca] Chemical compound [Fe].[Si].[Ca] CMFUZVSDFIHEAR-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012245 magnesium oxide Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010079 rubber tapping Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 2
- 239000011133 lead Substances 0.000 abstract description 35
- 229910052785 arsenic Inorganic materials 0.000 abstract description 28
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052709 silver Inorganic materials 0.000 abstract description 11
- 239000004332 silver Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052737 gold Inorganic materials 0.000 abstract description 10
- 239000010931 gold Substances 0.000 abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052787 antimony Inorganic materials 0.000 abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 description 49
- 239000000428 dust Substances 0.000 description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
- 238000004062 sedimentation Methods 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 14
- 239000002918 waste heat Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- UXNBTDLSBQFMEH-UHFFFAOYSA-N [Cu].[Zn].[Pb] Chemical compound [Cu].[Zn].[Pb] UXNBTDLSBQFMEH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052683 pyrite Inorganic materials 0.000 description 6
- 239000011028 pyrite Substances 0.000 description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- CNCDDMSQIDPLOW-UHFFFAOYSA-N [Au].[Zn].[Pb].[Cu] Chemical compound [Au].[Zn].[Pb].[Cu] CNCDDMSQIDPLOW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- SRJLIULHRSZVDI-UHFFFAOYSA-N oxolead;zinc Chemical compound [Zn].[Pb]=O SRJLIULHRSZVDI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a device and a method for comprehensively recovering and harmlessly treating valuable metal elements of copper smelting slag. The device comprises a first smelting unit, a second smelting unit and a negative pressure unit, wherein the first smelting unit comprises a first smelting furnace, a siliceous slag former supply unit, a first reducing agent supply unit and a first flue gas treatment unit, and the second smelting unit comprises a second smelting furnace, a calcareous slag former supply unit, a second reducing agent supply unit and a second flue gas treatment unit. By adopting the device, colored and black elements such as copper, lead, zinc, antimony, gold, silver, iron and the like in the copper smelting slag can be recovered, harmful elements such as arsenic and the like in the slag are deeply removed, the arsenic is enriched, and the comprehensive recovery of the colored elements and the black elements in the copper slag is realized. The generated tailings are similar to iron-making tailings in composition, are harmless tailings, and can be directly used for building materials. In a word, the method has the multiple advantages of high efficiency, short flow, low energy consumption, low cost, small occupied area, full recovery of valuable metal elements and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of copper smelting slag treatment, in particular to a device and a method for comprehensively recovering and harmlessly treating valuable metal elements of copper smelting slag.
Background
In the traditional copper smelting process, copper slag with 2.2-3 times of copper yield can be produced, and the copper content of the slag is about 1% -5%. Besides valuable elements copper, the slag contains zinc, lead, antimony, gold, silver, iron and other valuable elements, and the zinc content in the copper slag produced by partial enterprises is 2% -5%, and the existing copper slag treatment process mainly comprises slag beneficiation and electric furnace depletion processes.
The slag beneficiation process is to slowly cool copper slag, and then to separate slag concentrate through crushing, grinding, floatation and other processes to recover copper, wherein the copper content in the slag concentrate is generally 18-23%, and the copper content in tailings is less than 0.3%. And secondly, carrying out magnetic separation on the slag concentrate to separate iron concentrate. However, the process has long process flow, large occupied area and about 1/4 of the area of the copper smelting plant. In addition, valuable metals such as zinc and lead are difficult to recover in the copper recovery process, part of zinc is recovered into iron concentrate in the iron separation process, so that the iron concentrate contains higher zinc and is difficult to be used for blast furnace ironmaking, and the problem of low value of the iron concentrate is caused. However, the traditional electric furnace depletion technology has the defects that the tailings contain high copper (more than 0.6 percent), valuable metals such as lead and zinc cannot be recovered, 30-45 percent of iron-containing tailings are difficult to recover iron resources, and the iron resources are lost. Some copper slag treatment processes are also disclosed in the prior art, but all have obvious defects, such as:
In the Chinese patent of application number 201910053195.9, a method for treating copper slag is disclosed, but in the process of recovering copper, a large amount of iron enters copper matte, and alloy phase copper matte is crushed, finely ground, beneficiated and the like to obtain high-grade copper products and iron powder, but the copper content of the iron powder obtained by beneficiation is higher (more than 5%), and copper belongs to harmful impurity elements for part of steel types, so that the copper is cracked in the hot working process of steel, and therefore, the iron powder with too high copper content is difficult to use for steel smelting.
In the chinese patent of application No. 200910163234.7, a method for extracting iron by blowing, melting and reducing inert gas is disclosed, which avoids heat loss, but only considers the recovery of iron alone, does not consider the recovery and utilization problems of noble metals and copper, and does not consider impurities existing in iron.
The Chinese patent application No. 201210364451.4 discloses a method for preparing copper-rich alloy by oxidizing and desulfurizing hot copper slag and then blowing reducing agents such as natural gas and the like to recover copper and iron. The technology can be used for copper smelting slag obtained by smelting high-quality copper concentrate, but most of copper smelting slag contains elements such as lead, zinc, arsenic and the like, and is in the form of oxide in the copper slag. In the natural gas reduction process, most zinc and part of lead and arsenic elements can be reduced and volatilized, however, the impurity elements such as the rear part of lead and the like still enter the alloy along with copper, so that the impurity content of the alloy is high, and the product quality is affected.
In the Chinese patent of application number 201410345197.2, a method for directly smelting copper-containing antibacterial stainless steel by utilizing copper slag to reduce molten iron is disclosed, and the method is characterized in that firstly, the copper-containing molten iron is obtained through oxidation desulfurization and reduction, and is used for stainless steel smelting, but the scheme cannot solve the influence of lead-arsenic and other elements in slag on alloy distribution.
In the Chinese patent of application number 201910432636.6, a method for reducing and smelting copper-containing cast iron after settling and separating copper slag is disclosed, and the method utilizes the settling to obtain copper and precious metal recovery, and further ironmaking is carried out to obtain copper-containing molten iron. However, in the implementation process, valuable metals such as zinc and lead cannot be recovered, and the recovery rate of copper and noble metals is low, so that the copper content in the copper-containing pig iron is too high.
A technology for treating copper slag by a CR furnace is proposed in the patent of application number 201711433274.X of Enfei China, copper and zinc valuable metals in the slag are recovered, but the technology has the problem of low utilization rate of vulcanizing agents such as pyrite in the practical process, and the added auxiliary materials are pyrite and other vulcanizing agents, namely pyrite sedimentation is utilized to drive copper matte mixed in the slag to sediment, copper matte particles in the slag cannot be automatically settled, and the grade of the produced copper matte is low (15% -35%), so that the problems of large treatment capacity, low grade, high energy consumption and the like are caused in the subsequent copper matte smelting process. In addition, the process also has the problems of high sulfur content in the flue gas, lower smoke zinc grade, high flue gas treatment cost and the like, and the recovery of metal iron is not mentioned.
In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly aims to provide a device and a method for comprehensively recovering and harmlessly treating valuable metal elements in copper smelting slag, which are used for solving the problems that copper matte is low in grade, high in energy consumption, incapable of comprehensively recovering valuable metals and the like in copper smelting slag treatment in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a comprehensive recovery and innocent treatment device for valuable metal elements of copper smelting slag, comprising: a first smelting unit comprising: the first smelting furnace is provided with a first slag inlet, a first feeding hole, a first slag discharging hole, a copper discharging hole and a first smoke outlet, and is used for smelting copper smelting slag under the action of a first reducing agent and a siliceous slag former to obtain copper matte/copper alloy, first smoke and liquid iron-containing tailings; the siliceous slag former supply unit is connected with the first charging port and is used for providing siliceous slag formers for the first smelting furnace; a first reducing agent supply unit connected to the first charging port for supplying a first reducing agent into the first smelting furnace; the first flue gas treatment unit is connected with the first flue gas outlet and is used for treating the first flue gas discharged by the first flue gas treatment unit to obtain zinc-containing smoke dust or zinc-arsenic-containing smoke dust; a second smelting unit comprising: the second smelting furnace is provided with a second charging port, a second slag discharging port, an iron discharging port and a second smoke outlet, and is used for smelting the liquid iron-containing tailings under the action of a second reducing agent and a calcium slag former to obtain pig iron or ferrosilicon alloy, second smoke and harmless tailings; the calcium slag former supply unit is connected with the second charging port and is used for supplying calcium slag former to the second smelting furnace; a second reducing agent supply unit connected to the second charging port for supplying a second reducing agent to the second smelting furnace; the second flue gas treatment unit is connected with the second flue gas outlet and is used for treating the second flue gas discharged by the second flue gas treatment unit to obtain zinc-containing flue gas; the negative pressure unit is connected with the first smelting furnace and the second smelting furnace and is used for providing a negative pressure environment for the hearth in the smelting process of copper smelting slag and the smelting process of liquid iron-containing tailings; the first smelting furnace and the second smelting furnace are the same CR furnace, the first charging port is the second charging port, the first slag discharging port is the second slag discharging port, the copper discharging port is the iron discharging port, the first flue gas outlet is the second flue gas outlet, and the first flue gas treatment unit is the second flue gas treatment unit; or the first smelting furnace is a first CR furnace, the second smelting furnace is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, and the second smelting furnace is also provided with a first slag inlet which is connected with the first slag outlet.
Further, when the first smelting furnace and the second smelting furnace are the same CR furnace, the CR furnace is of a horizontal structure, and the side part of the CR furnace is also provided with air bricks and/or spray guns for introducing stirring gas into the slag layer in the smelting process of copper smelting slag and the smelting process of liquid iron-containing tailings; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; when the first smelting furnace is a first CR furnace and the second smelting furnace is a second CR furnace or an electric heating furnace, the first smelting furnace and the second smelting furnace are respectively and independently arranged in a horizontal structure, and the side parts of the first smelting furnace and the second smelting furnace are respectively and independently provided with air bricks and/or spray guns for introducing stirring gas into the slag layer in the respective smelting process; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; when the first smelting furnace is a first CR furnace and the second smelting furnace is a side-blown smelting furnace, the first smelting furnace and the second smelting furnace are respectively and independently arranged in a horizontal structure, and the side parts of the first smelting furnace and the second smelting furnace are respectively and independently provided with air bricks and/or spray guns for introducing stirring gas into the slag layer in the respective smelting process; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; simultaneously, the second smelting furnace is also provided with a fuel side-blowing spray gun for blowing fuel and oxygen-enriched air into the furnace to supply heat in the smelting process of the iron-containing tailings.
Further, the first slag inlet is formed in the top of the first smelting furnace and is close to one end of the first smelting furnace in the length direction, the first slag discharging port and the copper discharging port are formed in the side portion, away from the first slag inlet, of the other end of the first smelting furnace, and the air brick and/or the spray gun are arranged on the side wall, close to the first slag inlet, of the first smelting furnace.
Further, when the first smelting furnace is the first CR furnace, and the second smelting furnace is the second CR furnace, the electric heating furnace or the side-blown smelting furnace, in the second smelting furnace, the second slag inlet is arranged at the top of the second smelting furnace and is close to one end of the second smelting furnace in the length direction, the second slag outlet and the iron outlet are arranged at the side part of the other end of the second smelting furnace, which is far away from the second slag inlet, and the air brick and/or the spray gun are arranged on the side wall of the second smelting furnace, which is close to the second slag inlet.
Further, in the first smelting furnace, the shortest distance between the side wall where the copper placing port is located and the air brick and/or the spray gun along the length direction of the furnace body is L1, and the total length of the furnace body of the first smelting furnace is L, then L1/l=1/5-1/3.
Further, when the first smelting furnace is the first CR furnace and the second smelting furnace is the second CR furnace, the electric heating furnace or the side blowing smelting furnace, in the second smelting furnace, the shortest distance between the side wall of the iron notch and the air brick and/or the spray gun along the length direction of the furnace body is L1', and the total length of the furnace body of the second smelting furnace is L', then L1'/L' =1/5-1/3.
Further, in the first smelting furnace, a plurality of heating electrodes are arranged at the top of the first smelting furnace and are arranged above the slag layer where the air bricks and/or the spray gun are positioned; when the first smelting furnace is a first CR furnace and the second smelting furnace is a second CR furnace or an electric heating furnace, the top of the second smelting furnace is also provided with a plurality of heating electrodes which are arranged above the slag layer where the air bricks and/or the spray gun are positioned.
Further, when the first smelting furnace and the second smelting furnace are the same CR furnace, refractory bricks and copper water-cooling jackets are arranged in the side walls of the furnace body, wherein the refractory bricks are arranged on the side walls above the molten pool and the side walls corresponding to slag layers below the molten pool, one part of the copper water-cooling jackets are arranged between the upper refractory bricks and the lower refractory bricks and are in direct contact with the molten pool, and the other part of the copper water-cooling jackets are arranged between the lower refractory bricks and the side walls; or the refractory bricks are arranged on the whole side wall in the furnace body, and the copper water-cooling jacket is arranged on the corresponding side wall of the molten pool and is positioned between the refractory bricks and the side wall.
Further, when the first smelting furnace is a first CR furnace and the second smelting furnace is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, the inner parts of the side walls of the first smelting furnace and the second smelting furnace are respectively and independently provided with a fireproof furnace brick and a copper water cooling jacket; in the first smelting furnace, refractory bricks are arranged on the side wall above a molten pool and the side wall corresponding to a slag layer below the molten pool, and a copper water-cooling jacket is arranged between the upper refractory bricks and the lower refractory bricks and is in direct contact with the molten pool; or the refractory furnace bricks are arranged on the whole side wall in the furnace body, and the copper water-cooling jacket is arranged on the side wall corresponding to the molten pool and is positioned between the refractory furnace bricks and the side wall; in the second smelting furnace, refractory bricks are arranged on the side wall above the molten pool and the side wall corresponding to a slag layer below the molten pool, and a copper water-cooling jacket is arranged between the upper refractory bricks and the lower refractory bricks and is in direct contact with the molten pool; or the refractory bricks are arranged on the whole side wall in the furnace body, and the copper water-cooling jacket is arranged on the corresponding side wall of the molten pool and is positioned between the refractory bricks and the side wall.
Further, when the spray gun is provided, the siliceous slag former supply unit, the first reducing agent supply unit, the calcareous slag former supply unit, and the second reducing agent supply unit are each independently connected to the corresponding spray gun.
According to another aspect of the present invention, there is also provided a method for comprehensive recovery and innocent treatment of copper smelting slag, which is performed by using the apparatus for comprehensive recovery and innocent treatment of copper smelting slag, the method comprising the steps of: step S1, transferring copper smelting slag into a first smelting furnace, providing a siliceous slag former into the smelting furnace through a siliceous slag former supply unit, and providing a first reducing agent into the smelting furnace through a first reducing agent supply unit; smelting copper smelting slag under the action of a first reducing agent and a siliceous slag former in a first negative pressure state to obtain copper matte/copper alloy, first flue gas and liquid iron-containing tailings; processing the first flue gas by a first flue gas processing unit to obtain zinc-containing flue dust and zinc-arsenic-containing flue dust; step S2, supplying a calcareous slag former into a second smelting furnace through a calcareous slag former supply unit, and supplying a second reducing agent into the second smelting furnace through a second reducing agent supply unit; smelting the liquid iron-containing tailings under the action of a second reducing agent and a calcareous slag former in a second negative pressure state to obtain pig iron or ferrosilicon alloy, second flue gas and harmless tailings; treating the second flue gas by a second flue gas treatment unit to obtain zinc-containing flue dust; when the first smelting furnace and the second smelting furnace are the same CR furnace, after the step S1 is finished, discharging copper matte/copper alloy through a copper discharge port, and then executing the step S2; when the first smelting furnace is a first CR furnace and the second smelting furnace is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, after the step S1 is finished, transferring the liquid iron-containing tailings to the second smelting furnace through the first slag discharging port and the first slag inlet, and then executing the step S2.
Further, in the step S1, the slag type in the smelting process of the copper smelting slag is controlled to be FeO/SiO 2 =0.8 to 1.5, preferably FeO/SiO 2 =1 to 1.4; preferably, the siliceous slag former is selected from one or more of quartz stone, quartz, river sand and sea sand; preferably, the first reducing agent is one or more of coal, coke, petroleum coke, graphite, carbon powder, wood, ferrosilicon and elemental silicon; preferably, the particle size of the siliceous slag former is from 0.2 to 20mm and the particle size of the first reducing agent is from 1 to 30mm.
Further, in step S1, the operation temperature in the first smelting furnace is 1400-1600 ℃, preferably 1460-1550 ℃; the hearth operating pressure in the first smelting furnace is negative pressure of-10 to-300 Pa.
In step S1, inert gas and/or reducing gas are/is introduced into the slag layer through the air brick and/or the spray gun, and the ventilation volume of the single air brick or the spray gun is 1-100 Nm 3 /h; preferably, the first reductant and siliceous slag former are each fed independently through the lance and/or the first feed port when fed through the lance.
Further, in the step S2, the slag in the smelting process of the liquid iron-containing tailings is controlled to be CaO/SiO 2 Calcium-silicon slag or CaO/SiO of 0.8-1.2 2 0.3 to 0.6 of calcium-iron-silicon slag; preferably, the calcareous slag former is selected from one or more of calcium oxide, lime, limestone, magnesium oxide and dolomite; preferably, the second reducing agent is one or more of coal, coke, petroleum coke, graphite, ferrosilicon, elemental silicon and hydrogen; preferably, the particle size of the calcareous slag former is 0.2-20 mm and the particle size of the solid second reducing agent is 1-30 mm.
Further, in step S2, the operating temperature in the second smelting furnace is 1450-1650 ℃, preferably 1480-1550 ℃; the hearth operating pressure in the second smelting furnace is minus 5 Pa to minus 200Pa.
Further, in the step S2, inert gas and/or reducing gas is introduced into the slag layer through the air brick and/or the spray gun; preferably, the second reductant and the calcareous slag former are each fed independently through the lance and/or the second feed port when fed through the lance.
Further, in the step S2, when the second reducing agent and the calcareous slag former are added through the second feeding port, the ventilation volume of the single air brick or the spray gun is 1-100 Nm 3 /h; when the second reducing agent and the calcareous slag former are added through the spray gun, the ventilation volume of the single spray gun is 50-500 Nm 3 /h。
The device provided by the invention can be used for recovering copper, lead, zinc, antimony, gold, silver, iron and other colored and black elements in copper smelting slag, and deeply removing harmful elements such as arsenic in slag, so that arsenic is enriched, and the comprehensive recovery of the colored elements and the black elements in copper slag is realized. The generated tailings are similar to iron-making tailings in composition, are harmless tailings, and can be directly used for building materials. In a word, the device provided by the invention for treating copper smelting slag has the multiple advantages of high efficiency, short flow, low energy consumption, low cost, small occupied area, full recovery of valuable metal elements and environmental friendliness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a schematic structural diagram of a device for comprehensively recovering and harmlessly treating valuable metal elements in copper smelting slag according to one embodiment of the invention;
fig. 2 is a schematic structural view showing a device for comprehensively recovering and harmlessly treating valuable metal elements in copper smelting slag according to a second embodiment of the present invention;
fig. 3 is a schematic structural view showing a copper smelting slag valuable metal element comprehensive recovery and innocent treatment device according to a third embodiment of the present invention;
Fig. 4 is a schematic structural view showing a copper smelting slag valuable metal element comprehensive recovery and innocent treatment device according to a fourth embodiment of the present invention;
FIG. 5 shows the Gibbs free energy of reduction of a metal oxide value in copper smelting slag as a function of temperature.
Wherein the above figures include the following reference numerals:
10. a first smelting furnace; 101. a first slag inlet; 102. a first feed inlet; 103. a first slag discharging port; 104. a copper discharge port; 105. a first flue gas outlet; 11. a first flue gas treatment unit; 20. a second smelting furnace; 201. a second slag inlet; 202. a second feed inlet; 203. a second slag discharging port; 204. an iron discharging port; 205. a second flue gas outlet; 21. a second flue gas treatment unit; 12. refractory bricks; 13. a copper water cooling jacket; 111. a secondary combustion chamber; 112. a waste heat boiler; 113. a dust collection device; 114. a quenching unit; 111', a first secondary combustion chamber; 112', a first waste heat boiler; 113', a first dust collection device; 114', a first quench unit; 211. a second secondary combustion chamber; 212. a second waste heat boiler; 213. and a second dust collection device.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background art, the prior art for treating copper smelting slag by a CR furnace has the problem of low utilization rate of vulcanizing agents such as pyrite in the practical process, and the adding of the vulcanizing agents such as pyrite drives the slag to be mixed with copper matte by utilizing pyrite sedimentation, so that copper matte particles in the slag cannot be automatically settled, and the produced copper matte is low in grade (15% -35%), so that the problems of high treatment capacity, low grade, high energy consumption and the like are caused in the subsequent copper matte smelting process. In addition, the process also has the problems of high sulfur content in the flue gas, lower smoke zinc grade, high flue gas treatment cost and the like, and the recovery of metal iron is not mentioned. In a word, the problems of low grade of copper matte, high energy consumption, incapability of comprehensively recovering valuable metals and the like exist in the copper smelting slag treatment in the prior art.
In order to solve the problems, the inventor has proved through mechanism analysis and a large number of experimental researches that by adjusting slag, not adding auxiliary materials such as vulcanizing agent, controlling negative pressure and the like, the interfacial tension and the reaction atmosphere between slag and copper matte in the copper smelting slag smelting process can be regulated, thereby realizing the efficient and high-proportion recovery of copper zinc lead gold and silver and other colored elements, obtaining copper matte with copper grade of 60% -80%, copper alloy and zinc oxide with zinc content of more than 60%, and the produced tailings iron content of 35% -45%. And the liquid iron-containing tailings can be further smelted to obtain pig iron or ferrosilicon alloy by fully utilizing the residual heat of the tailings and combining with further slag regulation and control, and the iron recovery rate reaches more than 95 percent. Based on the method, the problems that zinc-containing iron concentrate obtained through mineral separation is difficult to use at a high value and the iron recovery rate is low are avoided; meanwhile, the produced pig iron can be directly used as steelmaking raw material or auxiliary material for steelmaking.
Based on the method, the invention provides a comprehensive recovery and harmless treatment device for valuable metal elements of copper smelting slag. As shown in fig. 1 to 4, the apparatus comprises a first smelting unit including a first smelting furnace 10, a siliceous slag former supply unit, a first reducing agent supply unit, and a first fume treatment unit 11, a second smelting unit including a second smelting furnace 20, a calcareous slag former supply unit, a second reducing agent supply unit, and a second fume treatment unit 21; the first smelting furnace 10 is provided with a first slag inlet 101, a first feeding hole 102, a first slag discharging hole 103, a copper discharging hole 104 and a first flue gas outlet 105, and the first smelting furnace 10 is used for smelting copper smelting slag under the action of a first reducing agent and a siliceous slag former to obtain copper matte/copper alloy, first flue gas and liquid iron-containing tailings; a siliceous slag former supply unit connected to the first charging port 102 for supplying a siliceous slag former to the first smelting furnace 10; the first reducing agent supply unit is connected to the first charging port 102 for supplying the first reducing agent into the first smelting furnace 10; the first flue gas treatment unit 11 is connected to the first flue gas outlet 105, and is used for treating the first flue gas discharged by the first flue gas treatment unit to obtain zinc-containing flue gas or zinc-arsenic-containing flue gas; the second smelting furnace 20 is provided with a second charging port 202, a second slag discharging port 203, an iron discharging port 204 and a second flue gas outlet 205, and the second smelting furnace 20 is used for smelting liquid iron-containing tailings under the action of a second reducing agent and a calcareous slag former to obtain pig iron or ferrosilicon alloy, second flue gas and harmless tailings; a calcium-based slag former supply unit connected to the second charging port 202 for supplying the calcium-based slag former to the second smelting furnace 20; a second reductant supply unit is connected to the second charging port 202 for supplying a second reductant to the second smelting furnace 20; the second flue gas treatment unit 21 is connected to the second flue gas outlet 205 and is used for treating the second flue gas discharged by the second flue gas treatment unit to obtain zinc-containing flue gas; the negative pressure unit is connected with the first smelting furnace 10 and the second smelting furnace 20 and is used for providing a negative pressure environment for the hearth in the smelting process of copper smelting slag and the smelting process of liquid iron-containing tailings;
As shown in fig. 1 and 2, the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, the first charging port 102 is the second charging port 202, the first slag tap 103 is the second slag tap 203, the copper tap 104 is the iron tap 204, the first flue gas outlet 105 is the second flue gas outlet 205, and the first flue gas processing unit 11 is the second flue gas processing unit 21; alternatively, as shown in fig. 3 and 4, the first smelting furnace 10 is a first CR furnace, the second smelting furnace 20 is a second CR furnace, an electric furnace, or a side-blown smelting furnace, and the second smelting furnace 20 is further provided with a first slag inlet 201 that is connected to the first slag tap 103.
The device provided by the invention can smelt liquid copper smelting slag under the action of the first reducing agent and the siliceous slag forming agent to obtain copper matte/copper alloy, first smoke and liquid iron-containing tailings, and then the liquid iron-containing tailings are subjected to iron recovery, so that the liquid copper smelting slag is smelted under the action of the second reducing agent and the calcareous slag forming agent to obtain pig iron or ferrosilicon alloy, second smoke and harmless tailings. The two-step process can be realized in a smelting furnace, namely a CR furnace; the smelting furnace can be realized by two smelting furnaces which are connected through a chute, for example.
Specifically, in the smelting process of copper smelting slag, a siliceous slag former is provided for the first smelting furnace 10 through a siliceous slag former supply unit, a first reducing agent is provided for the first smelting furnace 10 through a first reducing agent supply unit, and then a negative pressure unit is matched to enable a hearth of the first smelting furnace 10 to be in a negative pressure state, so that the slag viscosity can be effectively adjusted, the slag viscosity and copper matte (and copper alloy are discharged together, layering can be generated, the alloy is arranged at the upper part of the lower copper matte, and therefore interfacial tension and reaction atmosphere can be respectively collected), valuable elements such as copper, zinc, lead, antimony, gold and silver are fully recovered, and harmful elements such as arsenic are deeply removed. This is mainly due to: a large amount of iron in copper smelting slag exists as high-melting-point magnetic iron, so that part of silicon oxide exists as simple substance, the viscosity of the slag is high, copper matte microdrops are difficult to gather, grow and subside, and the sedimentation speed is low; according to the invention, the reducing agent is added to reduce the magnetic iron into FeO, so that slag is formed by adding the elemental silicon oxide and the added silicon oxide, the viscosity of the slag is reduced, and the sedimentation speed of copper matte is accelerated; and meanwhile, the slag viscosity can be reduced by adopting high-temperature smelting. The first slag former is added, and mainly because the silicon oxide content in the slag is increased, the interfacial tension of the slag is increased, and copper matte microdroplets in the slag are promoted to be stripped from the slag, so that the copper matte microdroplets are aggregated, grown and settled. Copper matte may be present as a separate phase in the copper slag. However, due to the reaction balance caused by the existence of activity, any two substances have a reaction trend, and a small amount of reaction can occur between copper matte and copper slag, so that a small amount of dissolved copper exists in the formed copper slag. FeO in copper smelting slag is alkaline substance, silicon oxide is acidic substance, the higher the alkalinity of copper slag is, the higher the free oxygen content in slag is, the better the reactivity of slag and copper matte is, and therefore the better the interface wettability of slag and copper is (i.e. the interface tension is low and separation is difficult). At high basicities, copper matte particles are therefore difficult to agglomerate and separate from the slag due to the better wettability with the copper slag (corresponding to lower interfacial tension). In the case of very low basicity, the free oxygen content in the slag is very low and the reactivity of the slag with copper matte is very weak, resulting in poor wettability (higher interfacial tension) between copper matte particles and slag. Under the condition of higher interfacial tension, copper matte particles tend to agglomerate and grow up and are separated from copper slag so as to reduce the free energy of the system.
The copper smelting slag comprises, but is not limited to, liquid copper smelting slag, blowing slag and other copper smelting intermediate slag, and optionally copper smelting smoke dust can be treated in a matching way. In the smelting process of the first smelting furnace 10, through adjustment of slag viscosity, interfacial tension with copper matte (and copper alloy) and reaction atmosphere, valuable metal elements such as copper, gold, silver and the like are separated from slag and settled to the bottom of a molten pool, elements such as zinc, lead, arsenic and the like are volatilized and discharged along with flue gas, and zinc-containing smoke dust (lead, zinc smoke dust) or zinc-arsenic smoke dust can be obtained through treatment of a first flue gas treatment unit. The step realizes the full separation and recovery of copper, zinc, lead, gold, silver and the like and iron, and simultaneously, as the invention does not need to add vulcanizing agent, the sulfur content in slag can be greatly reduced, and harmful elements such as arsenic and the like in slag are deeply removed.
After the copper smelting slag is smelted in the first smelting furnace 10, when the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, after the copper matte/copper alloy is discharged, a calcareous slag former and a second reducing agent can be continuously introduced into the copper matte/copper alloy, and the liquid iron-containing tailings are further smelted in a negative pressure state, so that the liquid iron-containing tailings are deeply reduced to recover iron resources in the liquid iron-containing tailings, and pig iron (or ferrosilicon alloy), second flue gas and harmless tailings are obtained. When the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electric heating furnace, or a side-blown smelting furnace, the liquid iron-containing tailings may be fed into the second smelting furnace 20 through a chute or the like for the above-described treatment. The oil valence elements such as zinc and lead which are not fully recovered in the first smelting process can be fully reduced and volatilized in the section, and the oil valence elements enter the second flue gas to be treated, so that zinc-containing smoke dust can be obtained, and the zinc and lead content in harmless tailings can be reduced to below 0.05%.
In a word, the device provided by the invention is used for treating copper smelting slag, so that the sectional and comprehensive recovery of valuable metal elements in the copper slag is realized, and high-quality zinc oxide, high-grade copper matte/copper alloy and low-copper pig iron/ferrosilicon alloy can be obtained; the process fully utilizes the waste heat of the copper slag, has low investment cost, low energy consumption, high efficiency and wide technical prospect, and is environment-friendly.
In a preferred embodiment, when the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, the CR furnace has a horizontal structure, and the side part of the CR furnace is further provided with air bricks and/or spray guns for introducing stirring gas into the slag layer during the smelting process of copper smelting slag and the smelting process of liquid iron-containing tailings; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace or an electric heating furnace, the first smelting furnace 10 and the second smelting furnace 20 are respectively and independently arranged in a horizontal structure, and the side parts of the first smelting furnace 10 and the second smelting furnace 20 are respectively and independently provided with air bricks and/or spray guns for introducing stirring gas into the slag layer in the respective smelting process; and the air brick and/or the spray gun are/is arranged at the position which is 1/10-9/10 of the height of the slag layer from the bottom of the slag layer. When the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a side-blown smelting furnace, the first smelting furnace 10 and the second smelting furnace 20 are respectively and independently in a horizontal structure, and the side parts of the first smelting furnace 10 and the second smelting furnace are respectively and independently provided with air bricks and/or spray guns for introducing stirring gas into the slag layer in the respective smelting process; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; meanwhile, the second smelting furnace 20 is further provided with a fuel side-blowing lance for blowing fuel (such as natural gas, coal dust, etc.) and oxygen-enriched air (oxygen concentration is greater than that in air, such as oxygen-enriched air with oxygen concentration of 30-98%) into the furnace in the smelting process of the iron-containing tailings to supply heat. By adopting the arrangement, stirring gas can be blown to the slag layer in the smelting process, so that the sedimentation recovery of copper matte/copper alloy (or pig iron and ferrosilicon alloy) is facilitated. During actual operation, the gas quantity of stirring gas can be controlled in a small gas quantity state, so that the high smoke dust rate caused by large gas quantity blowing measures is avoided, the zinc oxide grade is seriously influenced, and the sedimentation recovery of copper, gold, silver and the like is more facilitated. In addition, when a side-blown smelting furnace is used as the second smelting furnace, the reducing agent, heat and stirring kinetic energy can be supplied through the lance, thereby performing deep reduction.
In a preferred embodiment, the first slag notch 101 is provided at the top of the first smelting furnace 10 near one end in the length direction thereof, the first slag notch 103 and the copper notch 104 are provided at the other end side of the first smelting furnace 10 far from the first slag notch 101, and the air brick and/or the lance are provided on the side wall of the first smelting furnace 10 near the first slag notch 101. This arrangement can promote a more adequate smelting process. Similarly, in a preferred embodiment, when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electric heating furnace, or a side-blown smelting furnace, the second slag notch 201 is provided at the top of the second smelting furnace 20 near one end in the longitudinal direction thereof, the second slag notch 203 and the iron notch 204 are provided at the other end side of the second smelting furnace 20 away from the second slag notch 201, and the air brick and/or the lance are provided on the side wall of the second smelting furnace 20 near the second slag notch 201.
In order to fully separate the smelted slag layer from the lower layer and further improve the settling separation effect of the copper matte/copper alloy, in a preferred embodiment, in the first smelting furnace 10, the shortest distance between the side wall of the copper placing port 104 and the air brick and/or the spray gun along the length direction of the furnace body is L1, and the total length of the furnace body of the first smelting furnace 10 is L, then L1/l=1/5-1/3. Similarly, when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electrothermal furnace or a side-blown smelting furnace, in the second smelting furnace 20, the shortest distance between the sidewall of the tapping hole 204 and the air brick and/or the spray gun along the length direction of the furnace body is L1', and the total length of the furnace body of the second smelting furnace 20 is L', then L1'/L' =1/5-1/3. In the practical implementation process, preferably, 1 to 50 air bricks or small spray guns are arranged on the side walls of the first smelting furnace 10 and the second smelting furnace 20, and the single row is arranged in the length direction of the furnace body, for example, the spray guns are adopted, and the diameter of each spray gun is 1 to 30mm. The arrangement of the air brick and the spray gun mainly promotes the formation of slight stirring of a molten pool, improves the aggregation growth speed of copper matte microdroplets, improves the reaction speed of slag, slag forming agent and reducing agent, improves the volatilization speed of reduced zinc and lead, and reduces the proportion of lead sedimentation into copper matte. The arrangement is more beneficial to smelting copper smelting slag and is convenient for more fully separating copper, gold and silver from slag.
In a preferred embodiment, the first smelting furnace 10 is provided with a plurality of heating electrodes at the top thereof, which are arranged above the slag layer where the gas-permeable bricks and/or the lances are located; when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace or an electrothermal furnace, the top of the second smelting furnace 20 is also provided with a plurality of heating electrodes, which are arranged above the slag layer where the air bricks and/or the lances are located. Therefore, the electrode heating area and the stirring gas spraying area are correspondingly arranged, and smelting is more favorable to be fully carried out.
More preferably, when the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, refractory bricks 12 and a copper water-cooling jacket 13 are arranged inside the furnace body side walls, wherein, as shown in FIG. 1, the refractory bricks 12 are arranged on the side walls above a molten pool and the side walls corresponding to slag layers below the molten pool, a part of the copper water-cooling jacket 13 is arranged between the upper and lower refractory bricks and is in direct contact with the molten pool, and the other part of the copper water-cooling jacket 13 is arranged between the lower refractory bricks 12 and the side walls; alternatively, as shown in FIG. 2, the refractory bricks 12 are disposed on the entire side wall of the furnace body, and the copper water-cooling jacket 13 is disposed on the corresponding side wall of the bath between the refractory bricks 12 and the side wall. When the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, the inside of the side walls of the first smelting furnace 10 and the second smelting furnace 20 are respectively and independently provided with a refractory furnace brick 12 and a copper water-cooling jacket 13; in the first smelting furnace 10, as shown in fig. 3, refractory bricks 12 are arranged on the side wall above a molten pool and the side wall corresponding to a slag layer below the molten pool, and a copper water-cooling jacket 13 is arranged between the upper refractory bricks 12 and the lower refractory bricks and is in direct contact with the molten pool; alternatively, as shown in FIG. 4, the refractory bricks 12 are disposed on the entire side wall of the furnace body, and the copper water-cooling jackets 13 are disposed on the corresponding side wall of the molten bath between the refractory bricks 12 and the side wall; as shown in fig. 3, in the second smelting furnace 20, refractory bricks 12 are arranged on the side wall above the molten bath and the side wall corresponding to the slag layer below the molten bath, and a copper water-cooling jacket 13 is arranged between the upper and lower refractory bricks 12 and is in direct contact with the molten bath; alternatively, as shown in FIG. 4, the refractory bricks 12 are disposed on the entire side wall of the furnace body, and the copper water-cooling jacket 13 is disposed on the corresponding side wall of the bath between the refractory bricks 12 and the side wall.
Preferably, when the spray gun is provided, the siliceous slag former supply unit, the first reducing agent supply unit, the calcareous slag former supply unit, and the second reducing agent supply unit are each independently connected to the corresponding spray gun. In this way, the first reducing agent, the second reducing agent, the siliceous slag former and the calcareous slag former can be independently fed through a feeding port and/or a spray gun for blowing, and the operation is flexible and variable.
Preferably, when the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, the first flue gas and the second flue gas may share the same flue gas treatment unit, and as shown in fig. 1 and 2, the first flue gas treatment unit 11 includes a secondary combustion chamber 111, a waste heat boiler 112, a dust collecting device 113, and a quenching unit 114, which are sequentially communicated; when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, not shown in the figure, the two furnaces may share the same flue gas treatment unit, and may specifically include a secondary combustion chamber 111, a waste heat boiler 112, a dust collecting device 113 and a quenching unit 114 which are sequentially communicated; alternatively, as shown in fig. 3 and 4, the first flue gas treatment unit 11 includes a first secondary combustion chamber 111', a first waste heat boiler 112', a first dust collecting device 113', and a first quenching unit 114' which are sequentially communicated, and the second flue gas treatment unit 21 includes a second secondary combustion chamber 211, a second waste heat boiler 212, and a second dust collecting device 213 which are sequentially communicated. The arrangement is that the first flue gas can be subjected to secondary combustion, waste heat recovery and dust collection in sequence to obtain zinc-containing smoke dust and is quenched to obtain zinc-containing arsenic smoke dust, and the second flue gas can be subjected to secondary combustion, waste heat recovery and dust collection in sequence to obtain zinc-containing smoke dust. The four setting modes can be adopted, the cost is saved when the furnace is built in the first setting mode, the metal can be ensured not to contact the copper water jacket in the setting modes, and meanwhile furnace lining slag hanging can be realized.
For more uniform charging, preferably, the number of the first charging holes 102 is 1 to 20, and the first charging holes are distributed at the top of the furnace body, for example, are partially near the first slag inlet and partially between the electrodes. When two furnace bodies are adopted for treatment, the second smelting furnace can be a CR furnace or an electric heating furnace, and the electric heating furnace can be round, runway-shaped, rectangular, elliptic and the like. The two furnace bodies are preferably arranged in a stepped mode, namely the horizontal height of the second smelting furnace is lower than that of the first smelting furnace, and the two furnace bodies are connected through a chute, so that liquid iron-containing tailings can be conveniently transferred and fed.
According to another aspect of the present invention, there is also provided a method for comprehensive recovery and innocent treatment of copper smelting slag, which is performed by using the apparatus for comprehensive recovery and innocent treatment of copper smelting slag, the method comprising the steps of: step S1, transferring copper smelting slag into a first smelting furnace 10, providing a siliceous slag former into the smelting furnace through a siliceous slag former supply unit, and providing a first reducing agent into the smelting furnace through a first reducing agent supply unit; smelting copper smelting slag under the action of a first reducing agent and a siliceous slag former in a first negative pressure state to obtain copper matte/copper alloy, first flue gas and liquid iron-containing tailings; the first flue gas is treated by a first flue gas treatment unit 11 to obtain zinc-containing flue dust and zinc-arsenic-containing flue dust; step S2, supplying a calcareous slag former into the second smelting furnace 20 through a calcareous slag former supply unit, and supplying a second reducing agent into the second smelting furnace 20 through a second reducing agent supply unit; smelting the liquid iron-containing tailings under the action of a second reducing agent and a calcareous slag former in a second negative pressure state to obtain pig iron or ferrosilicon alloy, second flue gas and harmless tailings; treating the second flue gas by a second flue gas treatment unit 21 to obtain zinc-containing flue dust; wherein, when the first smelting furnace 10 and the second smelting furnace 20 are the same CR furnace, after the step S1 is finished, discharging copper matte/copper alloy through the copper discharge port 104, and then executing the step S2; when the first smelting furnace 10 is a first CR furnace and the second smelting furnace 20 is a second CR furnace, an electric heating furnace, or a side-blown smelting furnace, after the step S1 is completed, the liquid iron-containing tailings are transferred into the second smelting furnace 20 through the first slag tap 103 and the first slag inlet 201, and then the step S2 is performed.
The method provided by the invention is used for treating copper smelting slag, realizes the sectional and comprehensive recovery of valuable metal elements in the copper slag, and can obtain high-quality zinc oxide, high-grade copper matte/copper alloy and low-copper pig iron/ferrosilicon alloy; the process fully utilizes the waste heat of the copper slag, has low investment cost, low energy consumption, high efficiency and wide technical prospect, and is environment-friendly.
In the actual operation process, copper smelting slag can be transferred from a copper smelting furnace to the first smelting furnace 10 through a chute or a slag ladle, a first reducing agent and a siliceous slag former are added into the furnace through a belt or other modes according to a material mixing scheme according to metallurgical calculation, smelting in the first stage is carried out under the heating state of a heating electrode and the negative pressure condition, slag formation, copper matte/copper alloy sedimentation separation, selective reduction and volatilization of zinc, lead and arsenic are completed in the furnace, and part of iron is reduced. The obtained liquid iron-containing tailings have copper less than 0.4%, zinc less than 0.8%, lead less than 0.2% and arsenic less than 0.03%, and the copper grade of the obtained copper matte/copper alloy is higher and can reach 60% -80%. The obtained zinc-containing smoke dust has high zinc content, the zinc content is 65-80%, and the lead content is 5-20%. The recovery rate of gold and silver in the treated copper smelting slag can be more than 95 percent. The copper matte/copper alloy can directly enter a copper converting furnace or an anode furnace for smelting, and the high-quality zinc oxide can also be used for zinc-lead smelting.
The siliceous slag former participates in smelting in the first smelting furnace 10, silicon oxide exists in liquid slag in a molecular polyhedron, iron, calcium, magnesium and other oxides exist in an ionic state, the existence form of copper matte is similar to that of the iron, calcium, magnesium and other oxides, and the addition of silicon oxide can improve the interfacial tension of the copper matte and slag and promote the aggregation growth of copper matte microdroplets. In order to more fully exert the above effects and further improve the sedimentation separation effect of the copper matte/copper alloy, in a preferred embodiment, in step S1, the slag type in the copper smelting slag smelting process is controlled to be FeO/SiO 2 =0.8 to 1.5, preferably FeO/SiO 2 =1 to 1.4. Preferably, the siliceous slag former is rich in SiO 2 Such as one or more selected from quartz stone, quartz, river sand, sea sand.
The purpose of the first reducing agent is mainly two: (1) the existence of a large amount of iron in the copper slag as magnetic iron causes larger slag viscosity, and after the reducing agent is added, the magnetic iron is reduced into FeO and silicon oxide to form ferrous silicate by slag formation, so that the slag viscosity is reduced, and the copper matte sedimentation is promoted; (2) reducing the oxides of elements such as zinc, lead, arsenic and the like. Preferably, the first reducing agent is one or more of coal, coke, petroleum coke, graphite, carbon powder, wood, ferrosilicon, elemental silicon. For convenient feeding and more sufficient reaction, it is preferable that the particle size of the siliceous slag former is 0.2 to 20mm and the particle size of the first reducing agent is 1 to 30mm.
In a preferred embodiment, in step S1, the operating temperature in the first smelting furnace 10 is 1400-1600 ℃, preferably 1460-1550 ℃; the hearth operating pressure in the first smelting furnace 10 is negative pressure-10 to-300 Pa. The reason for adopting the operating temperature is that when the temperature reaches more than 1200 ℃, zinc oxide is reduced preferentially compared with iron oxide, the surplus temperature is more than 200 ℃, and the preferential reducibility is stronger. At the temperature, the first smelting furnace 10 can perform selective reduction more fully, and magnetic iron, zinc oxide, lead oxide and arsenic oxide in the slag are reduced preferentially to form FeO and elemental zinc, lead and arsenic, so that the deep removal of zinc, lead and arsenic is realized, the viscosity is reduced, and the full sedimentation separation of copper matte/copper alloy is realized. In particular, if the temperature is lower, a large amount of iron is reduced, so that the grade of copper matte is lower (the gibbs free energy of valuable metal oxide reduction in the copper smelting slag is changed along with the temperature as shown in fig. 5), and the temperature is controlled within the range, so that the grade of copper matte is improved more favorably. By adopting the negative pressure condition, the separation of slag and sulfonium is facilitated, the flue gas quantity is small, zinc and lead can be fully volatilized, and the grade of zinc in the formed zinc-containing smoke dust is higher. The negative pressure is too low, so that the partial pressure of zinc and lead in the hearth is too high, and volatilization of the reduced zinc and lead in the molten pool is not facilitated; the air leakage amount in the furnace is large due to the excessively high negative pressure, and a large amount of reducing agent is burnt by the air leakage, so that the utilization rate of the reducing agent is excessively low.
Preferably, the addition amount of the first reducing agent is 2.5-8% of that of copper smelting slag, so that the method is more beneficial to promoting the sedimentation and separation of valuable metals such as copper, gold, silver and the like in the form of copper matte/copper alloy, reducing and sedimentation of a small amount of iron, enabling elements such as zinc, lead, arsenic and the like to exist in the slag in the form of oxides, reducing the elements into simple substances to volatilize into flue gas after the reducing agent is added. Preferably, the power density of the heating electrode in the first smelting furnace is 50-500 kW/m 2 Preferably 150 to 400kW/m 2 。
In a preferred embodiment, in step S1, inert gas and/or reducing gas is introduced into the slag layer through the air bricks and/or the lance, and the ventilation volume of the air bricks or the lance is 1-100 Nm 3 And/h. In the first stage, that is, in the first smelting furnace 10, inert gas and/or reducing gas (as stirring gas) is introduced into the slag layer, but the blowing amount is not excessively large, so that strong stirring is caused, the smoke amount is excessively large, the zinc grade of zinc-rich smoke is greatly reduced, and meanwhile, the smoke amount is excessively large, so that heat is taken away, and the energy consumption is increased. The book is provided withThe invention selects slight stirring to accelerate the reaction speed of oxides such as zinc, lead, iron, arsenic and the like and the reducing agent, simultaneously promotes the aggregation and growth of copper matte microdrops and reduced metal iron microdrops, accelerates the sedimentation speed, can accelerate the volatilization of reduced zinc, lead simple substances, and reduces the amount of lead entering the copper matte. The inert gas includes, but is not limited to, nitrogen, argon, etc., and the reducing gas includes, but is not limited to, natural gas, coal gas, blast furnace gas, hydrogen, etc.
Preferably, the first reductant and siliceous slag former are each fed independently through the lance and/or first feed inlet 102 as they pass through the lance. The feeding form is flexible and adjustable, which is beneficial to adding materials in a dispersing way, improving the uniformity of the system and improving the smelting efficiency, and the method is understood by those skilled in the art and is not repeated here.
In the actual smelting process, copper smelting slag can continuously enter the first smelting furnace through a chute or intermittently enter the first smelting furnace; the siliceous slag former and the first reducing agent can continuously enter the first smelting furnace or intermittently enter the first smelting furnace; the first smelting furnace is internally provided with a sealing structure, so that the electrode burning loss is avoided seriously.
In the second stage, namely in the smelting process of the liquid iron-containing tailings, slag formation reduction is carried out under the action of a calcareous slag former and a second reducing agent, metal iron is reduced and settled, residual copper is reduced and settled along with the metal iron, and the unreduced oxides of zinc, lead and the like are further reduced and volatilized into smoke dust in the first stage. In order to further improve the slag-forming reduction effect, more preferably, in step S2, the slag type in the liquid iron-containing tailings smelting process is controlled to be a calcium-silicon slag type: caO/SiO 2 =0.8 to 1.2, or calcium iron silicon slag type: caO/SiO 2 =0.3 to 0.6. When the slag type is the former, the iron content of the produced tailings can be controlled to be less than 1%, and when the slag type is the latter, the iron content of the tailings is controlled to be 5-8%. After the second stage smelting, low copper pig iron (copper content is less than 0.7%, iron content is more than 96%), zinc-rich smoke dust (zinc content is more than 40%) and harmless pyrometallurgy tailings can be obtained.
The main function of the calcareous slag former is to slag silicon oxide in the liquid iron-containing tailings, improve the reduction trend of the iron oxide and promote the separation of slag and iron. To exert this effect more fully, preferably, the calcareous slag former is selected from one or more of calcium oxide, lime, limestone, magnesium oxide, dolomite; preferably, the second reducing agent is one or more of coal, coke, petroleum coke, graphite, ferrosilicon, elemental silicon and hydrogen; preferably, the particle size of the calcareous slag former is 0.2-20 mm and the particle size of the solid second reducing agent is 1-30 mm. Preferably, the addition amount of the second reducing agent is 10-30% of the weight of the liquid iron-containing tailings, so that deep recovery of iron, zinc and lead is realized, and harmless tailings (zinc content in the tailings is less than 0.05% and lead content is less than 0.05) are produced. In the actual production process, the obtained pig iron can be used for cast iron and cast steel production or used as scrap steel for steelmaking, and zinc-containing smoke dust is used for zinc-lead smelting recovery.
In a preferred embodiment, in step S2, the operating temperature in the second smelting furnace 20 is 1450-1650 ℃, preferably 1480-1550 ℃; the furnace operating pressure in the second smelting furnace 20 is minus 5 Pa to minus 200Pa. Under the condition, the iron slag separation can be carried out more fully, and the reduction and volatilization of the residual zinc oxide are promoted to form zinc-containing smoke dust. Especially under the negative pressure condition, the utilization rate of the second reducing agent is facilitated, the smoke amount is reduced, and the energy consumption is reduced.
Preferably, in step S2, inert gas and/or reducing gas is introduced into the slag layer through the air brick and/or the spray gun; preferably, the second reductant and the calcareous slag former are each fed independently through the lance and/or the second feed inlet 202 when fed through the lance. More preferably, in step S2, when the second reducing agent and the calcareous slag former are added through the second charging port 202, the ventilation amount of the single air brick or the lance is 1 to 100Nm 3 /h; when the second reducing agent and the calcareous slag former are added through the spray gun, the ventilation volume of the single spray gun is 50-500 Nm 3 /h。
The feeding mode of the second reducing agent and the calcium slag former is flexible and controllable, and the operation is convenient. Particularly when two smelting furnaces are adopted, in the second smelting furnace, the feeding modes of the calcareous slag former and the second reducing agent are mainly two kinds: (1) is added at the furnace top charging port 202, and 1 to 50 air bricks/small spray guns are arranged in the height direction of the slag layer, and a single row of air bricks/small spray guns are arranged Is arranged in the length direction of the furnace body, slightly agitates slag, and has the air volume of 1-100 Nm 3 And/h, the diameter of the spray gun is 1-30 mm; (2) 1-50 spray guns are arranged in the height direction of the slag layer, a single row of spray guns is arranged in the length direction of the furnace body, and the slag is slightly stirred, and the air quantity is 50-500 Nm3/h; the gas can be: inert gases such as nitrogen, argon and the like, and reducing gases such as natural gas, coal gas, blast furnace gas, hydrogen and the like can also be adopted; simultaneously, the second calcareous slag former and the second reducing agent are injected by a side-blowing spray gun (adopting concentrated phase conveying, preferably the solid-gas ratio is 1-40 kg/m) 3 )。
The first flue gas obtained in the treatment process is preferably subjected to secondary combustion treatment, waste heat recovery treatment and dust collection in sequence to obtain zinc-containing flue gas (the temperature is reduced to more than 250 ℃, zinc lead oxide is separated out first), and quenching to obtain zinc-containing arsenic flue gas (glass arsenic is generated when the temperature is too low in the quenching process); the second flue gas is preferably subjected to secondary combustion treatment, waste heat recovery treatment and dust collection in sequence to obtain zinc-containing smoke dust.
In a word, the device and the method for treating copper smelting slag have the following beneficial effects:
1. the CR furnace can be used for staged treatment, and the two smelting furnaces can be used for staged treatment; the equipment has the advantages of flexible characteristics, small investment, two steps of recycling metal elements in the slag, deeply removing harmful elements such as arsenic and the like, producing harmless fire tailings, and low cost, and the raw materials for treatment are liquid slag.
2. An air brick/small side blowing spray gun can be arranged to spray inert gas or reducing gas to slightly stir a molten pool, so that the reaction efficiency is improved, the aggregation growth and sedimentation speed of copper matte droplets are improved, and the volatilization of zinc and lead is accelerated;
3. the single smelting device and the two smelting devices are preferably electric heating treatment, so that the energy utilization rate is high, and the flue gas treatment cost is low; the two smelting devices can flexibly arrange the air brick, the small spray gun and the common spray gun according to the characteristics of the production process.
4. The smelting furnace can adopt a cooling water jacket to hang slag on a slag layer;
5. the electric heating is adopted as energy, so that the amount of smoke and dust can be greatly reduced, and the quality of smoke and dust can be improved.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in figure 1, and the process conditions are as follows:
treating 30 ten thousand tons of liquid copper smelting slag in a year, flowing the liquid copper smelting slag into a CR furnace through a chute, and adding coal and quartz stone into an auxiliary material charging hole, wherein the coal accounts for 5% of the slag and the quartz stone accounts for 4% of the slag; smelting temperature is 1450 ℃, smelting time is 2 hours, negative pressure is-50 Pa, no air brick/spray gun is arranged, and slag is Fe/SiO of ferrosilicon slag 2 =1.4, yielding 71% high-grade copper matte, 68% zinc oxide fume, arsenic fume, liquid iron-containing tailings (copper zinc lead reduced to 0.39%, 0.8%, 0.3%, respectively); adding 25% lime (liquid iron-containing tailings ratio), 18% coal (liquid iron-containing tailings ratio) and CaO/SiO as slag after discharging copper matte 2 =1, smelting temperature 1450 ℃, reducing and settling for 2 hours, and obtaining 40% zinc-rich smoke dust, wherein the iron content in tailings is 0.8%, and the iron content is 96% of molten iron.
Example 2
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in figure 1, and the process conditions are as follows:
treating 30 ten thousand tons of liquid copper smelting slag in a year, flowing the liquid copper smelting slag into a CR furnace through a chute, and adding coal and quartz stone into an auxiliary material charging hole, wherein the coal accounts for 5% of the slag and the quartz stone accounts for 4% of the slag; smelting temperature is 1450 ℃, smelting time is 1.5 hours, negative pressure is-50 Pa, and slag type is Fe/SiO of ferrosilicon slag 2 =1, 10 air bricks were set, each air brick blowing an air volume of 80Nm 3 And (3) producing 71% high-grade copper matte, zinc oxide smoke dust with zinc content of 66% and arsenic smoke dust, wherein the liquid iron-containing tailings (copper zinc lead is reduced to 0.32%, 0.5% and 0.2% respectively); adding 25% lime (liquid iron-containing tailings ratio), 18% coal (liquid iron-containing tailings ratio) and smelting temperature 1450 ℃ simultaneously after copper matte is discharged, reducing and settling for 2 hours, and obtaining CaO/SiO 2 =1, yield of 35% zinc-rich soot, iron content in tailings 0.6%, iron content 96% ironAnd (3) water.
Example 3
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in figure 1, and the process conditions are as follows:
treating 50 ten thousand tons of liquid copper smelting slag in a year, flowing the liquid copper smelting slag into a CR furnace through a chute, and adding coal and quartz stone into an auxiliary material charging hole, wherein the coal accounts for 5% of the slag and the quartz stone accounts for 4% of the slag; smelting temperature is 1500 ℃, smelting time is 2 hours, negative pressure is-50 Pa, and slag type is Fe/SiO of ferrosilicon slag 2 =1.2, no air brick/spray gun is set, 71% high-grade copper matte, zinc oxide smoke dust with zinc content of 66% and arsenic smoke dust are produced, and liquid iron-containing tailings (copper zinc lead is reduced to 0.35%, 0.55% and 0.25% respectively); adding 25% lime and 18% coal simultaneously after discharging copper matte, reducing and settling for 2h at 1500 ℃ and CaO/SiO 2 =1, yield obtained 38% zinc-rich smoke, iron content in tailings 0.7%, iron content 96% molten iron.
Example 4
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in figure 1, and the process conditions are as follows:
treating 50 ten thousand tons of liquid copper smelting slag annually, continuously flowing the liquid copper smelting slag into a CR furnace through a chute, and adding coal and quartz stone into an auxiliary material charging port, wherein the coal accounts for 6% of the slag and the quartz stone accounts for 3% of the slag; smelting temperature is 1500 ℃, smelting time is 2 hours, negative pressure is-50 Pa, and slag type is Fe/SiO of ferrosilicon slag 2 =0.8, no air brick/spray gun is arranged, and 70% high-grade copper matte, 69% zinc oxide smoke dust and arsenic smoke dust are produced, and the liquid iron-containing tailings (copper zinc lead is reduced to 0.4%, 0.6% and 0.22% respectively); adding 12% lime and 10% coal simultaneously after discharging copper matte, reducing and settling for 2h at 1500 ℃ and CaO/SiO 2 =0.5, yield obtained 42% zinc-rich fume, iron content 10% in tailings, iron content 95.5% molten iron.
Example 5
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in fig. 3, and the process conditions are as follows:
the annual treatment of 50 ten thousand tons of liquid copper smelting slag, and the continuous flow of the liquid copper smelting slag through a chuteAdding coal and quartz stone into a CR furnace at an auxiliary material charging port, wherein the coal accounts for 6% of slag and the quartz stone accounts for 4% of slag; smelting temperature is 1500 ℃, smelting time is 1.5 hours, negative pressure is-50 Pa, and slag type is Fe/SiO of ferrosilicon slag 2 =1.4, 15 air bricks were set, each air brick blowing an air volume of 60Nm 3 And (3) producing 73% of high-grade copper matte, 65% of zinc oxide smoke dust and arsenic smoke dust, and reducing the content of copper, zinc and lead to 0.3%, 0.35% and 0.15% respectively in the liquid iron-containing tailings; flowing the liquid iron-containing tailings into a second smelting furnace through a chute, adding 27% lime and 18% coal, reducing and settling for 2 hours at the smelting temperature of 1500 ℃ and adding CaO/SiO into the second smelting furnace 2 =1, 15 air bricks were set, and each air brick was blown with an air volume of 60Nm 3 And (3) producing 35% zinc-rich smoke dust, wherein the iron content in the tailings is 0.5%, and the iron content is 96% of molten iron.
Example 5
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in fig. 3, and the process conditions are as follows:
treating 50 ten thousand tons of liquid copper smelting slag annually, continuously flowing the liquid copper smelting slag into a CR furnace through a chute, and adding coal and quartz stone into an auxiliary material charging port, wherein the coal accounts for 4.5 percent of slag and the quartz stone accounts for 2 percent of slag; smelting temperature 1550 ℃, smelting time 1.5h, negative pressure-50 Pa, and slag type Fe/SiO of ferrosilicon slag 2 =1.4, 15 air bricks were set, each air brick blowing an air volume of 60Nm 3 And (3) producing 73% of high-grade copper matte, 65% of zinc oxide smoke dust and arsenic smoke dust, and reducing the liquid iron-containing tailings (copper zinc lead to 0.38%, 0.6% and 0.3% respectively); flowing the liquid iron-containing tailings into a second smelting furnace through a chute, adding 27% lime and 18% coal, reducing and settling for 2 hours at the smelting temperature of 1550 ℃ and CaO/SiO 2 =0.8, 15 air bricks were set, each air brick blowing an air volume of 60Nm 3 And (3) producing 45% zinc-rich smoke dust, wherein the iron content in tailings is 0.3%, and the iron content is 96% molten iron.
Example 6
The technology and the device are utilized to treat liquid copper smelting slag, the device is shown in fig. 3, and the process conditions are as follows:
the annual treatment of 50 ten thousand tons of liquid copper smelting slag, and the liquid copper smelting slag continuously flows into a chuteAdding coal and quartz stone into an auxiliary material charging port in a CR furnace, wherein the coal accounts for 7% of slag and the quartz stone accounts for 2% of slag; smelting temperature 1550 ℃, smelting time 1.5h, negative pressure-150 Pa, and slag type Fe/SiO of ferrosilicon slag 2 =1.4, 15 air bricks were set, each air brick blowing an air volume of 60Nm 3 And (3) producing 73% of high-grade copper matte, 65% of zinc oxide smoke dust and arsenic smoke dust, and reducing the liquid iron-containing tailings (copper zinc lead to 0.38%, 0.6% and 0.3% respectively); flowing the liquid iron-containing tailings into a second smelting furnace through a chute, adding 27% lime and 18% coal, reducing and settling for 2 hours at the smelting temperature of 1550 ℃ and CaO/SiO 2 =0.8, 15 air bricks were set, each air brick blowing an air volume of 60Nm 3 And (3) producing 45% zinc-rich smoke dust, wherein the iron content in tailings is 0.3%, and the iron content is 96% molten iron.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. The utility model provides a copper smelting sediment valuable metal element comprehensive recovery and innocent treatment device which characterized in that includes:
a first smelting unit comprising:
the first smelting furnace (10) is provided with a first slag inlet (101), a first feeding hole (102), a first slag discharging hole (103), a copper discharging hole (104) and a first flue gas outlet (105), wherein the first smelting furnace (10) is used for smelting copper smelting slag under the action of a first reducing agent and a siliceous slag former to obtain copper matte/copper alloy, first flue gas and liquid iron-containing tailings;
a siliceous slag former supply unit connected to said first charging port (102) for supplying said siliceous slag former to said first smelting furnace (10);
a first reducing agent supply unit connected to the first charging port (102) for supplying the first reducing agent into the first smelting furnace (10);
a first flue gas treatment unit (11) connected to the first flue gas outlet (105) for treating the first flue gas discharged therefrom to obtain zinc-containing flue dust or zinc-arsenic-containing flue dust; a second smelting unit comprising:
a second smelting furnace (20) provided with a second charging port (202), a second slag discharging port (203), a tapping port (204) and a second flue gas outlet (205), wherein the second smelting furnace (20) is used for leading the liquid iron-containing tailings to be in a state of
Smelting under the action of a second reducing agent and a calcareous slag former to obtain pig iron or ferrosilicon alloy, second flue gas and harmless tailings;
a calcareous slag former supply unit connected to the second charging port (202) for supplying the calcareous slag former to the second smelting furnace (20);
a second reducing agent supply unit connected to the second charging port (202) for supplying the second reducing agent to the second smelting furnace (20);
a second flue gas treatment unit (21) connected to the second flue gas outlet (205) for treating the second flue gas discharged therefrom to obtain zinc-containing flue gas; the negative pressure unit is connected with the first smelting furnace (10) and the second smelting furnace (20) and is used for providing a negative pressure environment for a hearth in the smelting process of the copper smelting slag and the smelting process of the liquid iron-containing tailings;
the first smelting furnace (10) and the second smelting furnace (20) are the same CR furnace, the first charging port (102) is the second charging port (202), the first slag discharging port (103) is the second slag discharging port (203), the copper discharging port (104) is the iron discharging port (204), the first flue gas outlet (105) is the second flue gas outlet (205), and the first flue gas treatment unit (11) is the second flue gas treatment unit (21); or, the first smelting furnace (10) is a first CR furnace, the second smelting furnace (20) is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, and the second smelting furnace (20) is also provided with a second slag inlet (201) which is connected with the first slag outlet (103).
2. The apparatus of claim 1, wherein the device comprises a plurality of sensors,
when the first smelting furnace (10) and the second smelting furnace (20) are the same CR furnace, the CR furnace is of a horizontal structure, and the side part of the CR furnace is also provided with air bricks and/or spray guns for introducing stirring gas into a slag layer in the smelting process of the copper smelting slag and the smelting process of the liquid iron-containing tailings; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer;
when the first smelting furnace (10) is the first CR furnace and the second smelting furnace (20) is the second CR furnace or the electric heating furnace, the first smelting furnace (10) and the second smelting furnace (20) are respectively and independently of a horizontal structure, and the side parts of the two smelting furnaces are respectively and independently provided with an air brick and/or a spray gun for introducing stirring gas into a slag layer in the respective smelting process; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer;
when the first smelting furnace (10) is the first CR furnace and the second smelting furnace (20) is the side-blown smelting furnace, the first smelting furnace (10) and the second smelting furnace (20) are respectively and independently of a horizontal structure, and the side parts of the two smelting furnaces are respectively and independently provided with air bricks and/or spray guns for introducing stirring gas into a slag layer in the respective smelting process; the air brick and/or the spray gun are/is arranged at the position 1/10-9/10 of the slag layer height from the bottom of the slag layer; simultaneously, the second smelting furnace (20) is also provided with a fuel side-blowing spray gun for blowing fuel and oxygen-enriched air into the furnace to supply heat in the smelting process of the iron-containing tailings.
3. The apparatus of claim 2, wherein the device comprises a plurality of sensors,
the first slag inlet (101) is formed in the top of the first smelting furnace (10) and is close to one end of the first smelting furnace in the length direction, the first slag discharging port (103) and the copper discharging port (104) are formed in the side portion, far away from the first slag inlet (101), of the other end of the first smelting furnace (10), and the air brick and/or the spray gun are arranged on the side wall, close to the first slag inlet (101), of the first smelting furnace (10).
4. A device according to claim 2 or 3, wherein,
when the first smelting furnace (10) is the first CR furnace, the second smelting furnace (20) is the second CR furnace, the electric heating furnace or the side-blown smelting furnace, in the second smelting furnace (20), the second slag inlet (201) is arranged at the top of the second smelting furnace (20), and one end, close to the length direction, of the second smelting furnace (20) is arranged, the second slag outlet (203) and the iron outlet (204) are arranged at the side part, far away from the other end of the second slag inlet (201), of the second smelting furnace (20), and the air brick and/or the spray gun are arranged on the side wall, close to the second slag inlet (201), of the second smelting furnace (20).
5. The apparatus according to claim 4, wherein in the first smelting furnace (10), the shortest distance between the side wall of the copper placing port (104) and the air brick and/or the spray gun along the length direction of the furnace body is L1, and the total length of the furnace body of the first smelting furnace (10) is L, L1/l=1/5-1/3.
6. The apparatus according to claim 5, wherein when the first smelting furnace (10) is the first CR furnace, the second smelting furnace (20) is the second CR furnace, the electrothermal furnace or the side-blown smelting furnace, in the second smelting furnace (20), a shortest distance between a sidewall of the tapping hole (204) and an air brick and/or a lance along a length direction of the furnace body is L1', and a total length of the furnace body of the second smelting furnace (20) is L', and L1'/L' =1/5-1/3.
7. The apparatus according to claim 4, characterized in that in the first smelting furnace (10) a plurality of heating electrodes are arranged on top of it, which are arranged above the slag layer where the gas-permeable bricks and/or lances are located; when the first smelting furnace (10) is the first CR furnace, the second smelting furnace (20) is the second CR furnace or the electric heating furnace, a plurality of heating electrodes are also arranged at the top of the second smelting furnace (20), and the heating electrodes are arranged above the slag layer where the air bricks and/or the spray gun are positioned.
8. The apparatus according to claim 1, wherein when the first smelting furnace (10) and the second smelting furnace (20) are the same CR furnace, the furnace body side wall is internally provided with a refractory furnace brick (12) and a copper water-cooling jacket (13), wherein,
The refractory furnace bricks (12) are arranged on the side wall above the molten pool and the side wall corresponding to the slag layer below the molten pool, one part of the copper water-cooling jacket (13) is arranged between the upper refractory furnace bricks and the lower refractory furnace bricks and is in direct contact with the molten pool, and the other part of the copper water-cooling jacket (13) is arranged between the lower refractory furnace bricks (12) and the side wall; or,
the refractory furnace bricks (12) are arranged on the whole side wall in the furnace body, and the copper water-cooling jacket (13) is arranged on the side wall corresponding to the molten pool and is positioned between the refractory furnace bricks (12) and the side wall.
9. The apparatus according to claim 1, characterized in that when the first smelting furnace (10) is the first CR furnace and the second smelting furnace (20) is the second CR furnace, the electrothermal furnace or the side-blown smelting furnace, the inside of the side walls of the first smelting furnace (10) and the second smelting furnace (20) are each provided with a refractory furnace brick (12) and a copper water-cooled jacket (13) independently; wherein,,
in the first smelting furnace (10), the refractory furnace bricks (12) are arranged on the side wall above the molten pool and the side wall corresponding to the slag layer below the molten pool, and the copper water-cooling jacket (13) is arranged between the upper refractory furnace bricks (12) and the lower refractory furnace bricks and is in direct contact with the molten pool; or the refractory furnace bricks (12) are arranged on the whole side wall in the furnace body, and the copper water-cooling jackets (13) are arranged on the side wall corresponding to the molten pool and are positioned between the refractory furnace bricks (12) and the side wall;
In the second smelting furnace (20), the refractory furnace bricks (12) are arranged on the side wall above the molten pool and the side wall corresponding to the slag layer below the molten pool, and the copper water-cooling jacket (13) is arranged between the upper refractory furnace bricks (12) and the lower refractory furnace bricks and is in direct contact with the molten pool; or the refractory furnace bricks (12) are arranged on the whole side wall in the furnace body, and the copper water-cooling jackets (13) are arranged on the side wall corresponding to the molten pool and are positioned between the refractory furnace bricks (12) and the side wall.
10. The apparatus of claim 4, wherein when a lance is provided, the siliceous slag former supply unit, the first reductant supply unit, the calcareous slag former supply unit, and the second reductant supply unit are each independently connected to a corresponding lance.
11. A method for comprehensively recovering and harmlessly treating valuable metal elements in copper smelting slag, which is characterized by adopting the device for comprehensively recovering and harmlessly treating the valuable metal elements in the copper smelting slag according to any one of claims 1 to 10, and comprising the following steps:
step S1, transferring copper smelting slag into a first smelting furnace (10), providing a siliceous slag former into the smelting furnace through a siliceous slag former supply unit, and providing a first reducing agent into the smelting furnace through a first reducing agent supply unit; smelting the copper smelting slag under the action of the first reducing agent and the siliceous slag forming agent in a first negative pressure state to obtain copper matte/copper alloy, first flue gas and liquid iron-containing tailings; treating the first flue gas by a first flue gas treatment unit (11) to obtain zinc-containing flue dust and zinc-arsenic-containing flue dust;
Step S2, supplying a calcareous slag former into a second smelting furnace (20) through a calcareous slag former supply unit, and supplying a second reducing agent into the second smelting furnace (20) through a second reducing agent supply unit; under a second negative pressure state, smelting the liquid iron-containing tailings under the action of the second reducing agent and the calcareous slag former to obtain pig iron or ferrosilicon alloy, second flue gas and harmless tailings; treating the second flue gas by a second flue gas treatment unit (21) to obtain zinc-containing flue dust;
when the first smelting furnace (10) and the second smelting furnace (20) are the same CR furnace, after the step S1 is finished, discharging the copper matte/copper alloy through a copper discharge port (104), and then executing the step S2; when the first smelting furnace (10) is a first CR furnace and the second smelting furnace (20) is a second CR furnace, an electric heating furnace or a side-blown smelting furnace, after the step S1 is finished, transferring the liquid iron-containing tailings into the second smelting furnace (20) through a first slag discharging port (103) and a first slag inlet (201), and then executing the step S2.
12. The method according to claim 11, wherein in the step S1, the slag type in the copper smelting slag smelting process is controlled to be FeO/SiO 2 =0.8 to 1.5, preferably FeO/SiO 2 ＝1～1.4；
Preferably, the siliceous slag former is selected from one or more of quartz stone, quartz, river sand and sea sand;
preferably, the first reducing agent is one or more of coal, coke, petroleum coke, graphite, carbon powder, wood, ferrosilicon and elemental silicon;
preferably, the particle size of the siliceous slag former is 0.2-20 mm and the particle size of the first reducing agent is 1-30 mm.
13. The method according to claim 11 or 12, characterized in that in step S1 the operating temperature in the first smelting furnace (10) is 1400-1600 ℃, preferably 1460-1550 ℃; the hearth operation pressure in the first smelting furnace (10) is negative pressure-10 to-300 Pa.
14. The method according to claim 13, wherein in the step S1, inert gas and/or reducing gas is introduced into the slag layer through the air brick and/or the lance, and the ventilation amount of the air brick or the lance is 1-100 Nm 3 /h; preferably, the first reductant and the siliceous slag former are each fed independently through the lance and/or the first feed inlet (102) when fed through the lance.
15. The method according to claim 11, wherein in the step S2, the slag type in the liquid iron-containing tailings smelting process is controlled to be CaO/SiO 2 ＝0.8～1.2 calcium-silicon slag or CaO/SiO 2 0.3 to 0.6 of calcium-iron-silicon slag;
preferably, the calcareous slag former is selected from one or more of calcium oxide, lime, limestone, magnesium oxide and dolomite;
preferably, the second reducing agent is one or more of coal, coke, petroleum coke, graphite, ferrosilicon, elemental silicon and hydrogen;
preferably, the particle size of the calcareous slag former is 0.2-20 mm, and the particle size of the solid second reducing agent is 1-30 mm.
16. The method according to claim 11 or 15, characterized in that in step S2 the operating temperature in the second smelting furnace (20) is 1450-1650 ℃, preferably 1480-1550 ℃; the hearth operating pressure in the second smelting furnace (20) is minus 5 Pa to minus 200Pa.
17. The method according to claim 16, wherein in step S2, inert gas and/or reducing gas is introduced into the slag layer through the gas permeable bricks and/or the lance; preferably, the second reductant and the calcareous slag former are each fed independently through the lance and/or the second feed inlet (202) when fed through the lance.
18. The method according to claim 17, characterized in that in step S2, when the second reducing agent and the calcareous slag former are added through the second feed opening (202), the ventilation of the single air brick or lance is 1-100 Nm 3 /h; when the second reducing agent and the calcium slag former are added through the spray gun, the ventilation volume of the single spray gun is 50-500 Nm 3 /h。
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