CN105603198A - Resource recycling method of high-impurity-content copper smelting slag - Google Patents
Resource recycling method of high-impurity-content copper smelting slag Download PDFInfo
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- CN105603198A CN105603198A CN201610084769.5A CN201610084769A CN105603198A CN 105603198 A CN105603198 A CN 105603198A CN 201610084769 A CN201610084769 A CN 201610084769A CN 105603198 A CN105603198 A CN 105603198A
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- CN
- China
- Prior art keywords
- oxygen
- copper
- copper smelting
- smelting slag
- refining furnace
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- 239000002893 slag Substances 0.000 title claims abstract description 367
- 239000010949 copper Substances 0.000 title claims abstract description 344
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 343
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 341
- 238000003723 Smelting Methods 0.000 title claims abstract description 277
- 238000000034 method Methods 0.000 title claims abstract description 111
- 238000004064 recycling Methods 0.000 title abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 215
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 215
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 214
- 238000007670 refining Methods 0.000 claims abstract description 207
- 239000012535 impurity Substances 0.000 claims abstract description 194
- 239000007789 gas Substances 0.000 claims abstract description 149
- 230000003647 oxidation Effects 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 72
- 230000008569 process Effects 0.000 claims abstract description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 238000005188 flotation Methods 0.000 claims description 55
- 239000002737 fuel gas Substances 0.000 claims description 50
- 239000012141 concentrate Substances 0.000 claims description 43
- 229910052785 arsenic Inorganic materials 0.000 claims description 37
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 34
- 238000012545 processing Methods 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 32
- 229910052787 antimony Inorganic materials 0.000 claims description 31
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 31
- 229910052797 bismuth Inorganic materials 0.000 claims description 31
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 29
- 229910052718 tin Inorganic materials 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000002485 combustion reaction Methods 0.000 claims description 25
- 238000010583 slow cooling Methods 0.000 claims description 22
- 229960004643 cupric oxide Drugs 0.000 claims description 21
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 20
- 240000005373 Panax quinquefolius Species 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 102000010637 Aquaporins Human genes 0.000 claims description 18
- 108010063290 Aquaporins Proteins 0.000 claims description 18
- 238000007885 magnetic separation Methods 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 238000009533 lab test Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000013461 design Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 239000000567 combustion gas Substances 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000011819 refractory material Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 14
- 229910001779 copper mineral Inorganic materials 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 229910001608 iron mineral Inorganic materials 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007664 blowing Methods 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract description 2
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910052595 hematite Inorganic materials 0.000 abstract 1
- 239000011019 hematite Substances 0.000 abstract 1
- 238000012546 transfer Methods 0.000 description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 description 17
- 239000011707 mineral Substances 0.000 description 17
- 239000000956 alloy Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 239000012943 hotmelt Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000032258 transport Effects 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 5
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002927 oxygen compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 229910052840 fayalite Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000033764 rhythmic process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 238000003672 processing method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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
- C22B15/0054—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
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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 discloses a resource recycling method of high-impurity-content copper smelting slag. The process of removing impurity elements in the copper smelting slag is achieved by re-blowing outside oxygen-containing gas in a vacuum state inside a refining furnace, and the impurity elements in the copper smelting slag is removed to facilitate production of higher-purity higher-quality down-stream products; then the impurity elements are recovered in an oxide state to obtain a condensed-state oxide mixture of the impurity elements, and the mixture is sold out in the form of a metal product. According to the resource recycling method, various copper minerals are converted into a copper oxide phase and various iron minerals are converted into a hematite phase by fully oxidizing the hot-melting copper smelting slag, wholly oxidizing the copper minerals and iron minerals and conducting oxidation separation on mixed copper and iron minerals to facilitate follow-up copper, iron and silicon recovery by adopting a beneficiation treatment process; economic benefits are brought to copper smelting enterprises, the earning capacity of the copper smelting enterprises is improved, meanwhile resource waste is reduced, and environmental pollution is reduced.
Description
Technical field
The present invention relates to resource and reclaim environmental technology field, the resource that especially relates to a kind of high impurity copper metallurgical slag reclaimsMethod.
Background technology
In copper smelting industry, carry copper and conventionally adopt the method for pyrometallurgy from copper sulfide concentrate, its flow process is generally: sulphurChange Copper Ores → selecting and purchasing operation → copper concentrate → melting operation → matte+smelting slag → blowing operation → blister copper+blowing slag →Anode refining operation → anode copper → electrorefining operation → Cu-CATH-1.
Copper smelting slag is included in copper and smelts the multiple slag of output in production process, and the overwhelming majority is smelting slag, also has small partBlowing slag etc. Wherein copper smelting slag mainly comprises 0.90%～3.0% Cu, 35%～44% Fe, 25%～35%SiO2。
Copper smelting slag processing intent is now the copper reclaiming in copper smelting slag, the slag essence that output copper content is higherOre deposit (a kind of copper concentrate producing that reclaims from slag), in copper smelting slag, original iron, silicon etc. remain in mine tailing, as solidBody discarded object is applied in the industries such as building trade. Along with technological progress, indivedual forward positions patented technology proposes the smelting of modified copperRefining slag processing method, in output slag concentrate, output iron ore concentrate and higher SO2The siliceous product of content.
As everyone knows, in copper smelting slag, also comprise the impurity elements such as lead, zinc, arsenic, antimony, bismuth and/or tin. This part is assortedPrime element derives from the copper concentrate that drops into smelting furnace. Smelt the element balance angle calculation of flow process from whole copper, smeltingCheng Zhong, the impurity element in raw copper concentrate very major part has entered in copper smelting slag, wherein, enters in copper smelting slagImpurity element ratio maximum.
This part impurity element, on the one hand, the iron ore concentrate of institute output and siliceous product after affecting subsequent copper metallurgical slag and processingQuality and purity, for example: the impurity elements such as lead, zinc, arsenic, antimony, bismuth and tin are in iron ore concentrate in strict limited contentThe element kind of limit, has carried out strict classification requirement, impurity element meeting to the impurity content in iron ore concentrate in GBTo the negative influence of ironmaking processes and steelmaking process generation highly significant, have a strong impact on production process, equipment life and productProduct quality etc.
On the other hand, mention impurity element, habitually thinking of industry technology personnel is that " bad thing is removed as far as possibleThing ", hardly realize, change a thought angle, this part impurity element is also a kind of resource that can produce economic benefit.If copper smelting enterprise reclaims this part impurity element preferably, then sell outward with the form of metal product, and sell the moon outwardUtmost point copper coin is the same, also can produce significant economic benefit. At present, also there is not prior art propose in copper smelting slagThis part impurity element reclaims.
To sum up, current copper smelting slag processing method, and the modified copper smelting slag processing of mentioning in the patented technology of forward positionMethod, does not all consider the problem of a large amount of impurity elements contained in copper smelting slag. This part impurity element had both been given existing productProduct quality is brought very large negative influence, expends ample resources and the energy, improves the production cost of Liao Tong smelting enterprise,Do not bring into play again itself intrinsic economic worth, not for copper smelting enterprise brings due economic benefit, be on one sideCost raises, and is there is no output economic benefit on one side, and both sides are added, and has brought to the economic profit space of copper smelting enterpriseSignificant negative influence, reduces the profitability of Liao Tong smelting enterprise.
Moreover in recent years, along with the develop rapidly of copper smelting industry, old smeltery and new smelter are tapped the potential and upgrade technologically copper are producedAmount increases very fast, and this trend also can be sustained, and causes the supply of high-quality copper concentrate to become more and more nervous.For Mai Kuang enterprise, the copper concentrate of buying high-quality is more much higher than the impure high copper concentrate cost of buying. Therefore,Copper smelting enterprise is from self benefit, and the raw material of buying becomes and becomes increasingly complex, and impurity component is more and more higher, mainly containsThe impurity elements such as lead, zinc, arsenic, antimony, bismuth, tin. The copper concentrate that impurity content is high is more cheap than the copper concentrate price of high-qualityTo a certain degree, impurity content is higher, and copper concentrate is more cheap. After these high impurity copper concentrate put into production, carry furtherHigh impurity content in copper smelting slag. According to above-mentioned, change a thought angle, impurity element is also a kind of resource,Also can produce economic benefit, if copper smelting enterprise purchases high impurity copper concentrate with lower price, then, then by itIn contained impurity element sell outward with the form of metal product, output economic benefit, one-in-and-one-out, two combination, both fellLow cost of material, has increased again extra income, and this will improve the profitability of copper smelting enterprise significantly, thisFor the copper smelting industry of current depression, will be a management mode with very large attraction.
Therefore, how the impurity element in copper smelting slag is removed and is beneficial to the more better downstream of high-quality product of output purityProduct, reclaim impurity element to sell with the form of metal product outward simultaneously, and for copper, smelting enterprise brings economic benefit, improve copperThe profitability of smelting enterprise reduces the wasting of resources simultaneously, and reducing environmental pollution is that those skilled in the art need solution badlyTechnical problem.
Summary of the invention
Based on above-mentioned explanation, the object of the present invention is to provide a kind of resource recycle method of high impurity copper metallurgical slag, shouldMethod can remove the impurity element in copper smelting slag and be beneficial to the more better downstream product of high-quality of output purity, simultaneouslyImpurity element is reclaimed and sold outward with the form of metal product, and for copper, smelting enterprise brings economic benefit, improves copper smelting enterpriseProfitability, reduce the wasting of resources simultaneously, reduce environmental pollution.
For solving above-mentioned technical problem, the present invention adopts following technical scheme:
A resource recycle method for high impurity copper metallurgical slag, comprises the following steps:
1) the copper smelting slag liquation of melting is joined to the Sheng slag container for splendid attire copper smelting slag liquation; Then will establishPut upper liquid level that feed tube on refining furnace diapire and drain pipe be immersed in copper smelting slag liquation in described Sheng slag container withLower certain depth, then opens the vavuum pump that is communicated with described refining furnace by the shape that is evacuated of the cavity in described refining furnaceState, now in refining furnace under the effect of the atm difference between vacuum residual voltage and external atmosphere pressure in described Sheng slag containerCopper smelting slag liquation rises and flows in the cavity of described refining furnace along the cavity passage in described feed tube and described drain pipe;
The profile of described refining furnace is vertical column, inner hollow form cavity, described refining furnace comprise steel shell andBuild the refractory lining at described steel shell inner surface by laying bricks or stones, the top of described refining furnace be provided with for described vacuumThe gas outlet that pump connects;
Described feed tube and described drain pipe include steel inner casing, are arranged on the fire proofed wood of the inner surface of described steel inner casingExpect liner and be arranged on the refractory material outer lining of the outer surface of described steel inner casing;
Described feed tube and described drain pipe be fixedly installed on the diapire of described refining furnace and with the diapire of described refining furnaceBe tightly connected, the cavity passage in the cavity in described refining furnace and described feed tube is interconnected, in described refining furnaceCavity passage in cavity and described drain pipe is interconnected, the device that all and described refining furnace is connected with described refiningEncapsulation process is all carried out to prevent from destroying the vacuum state in described refining furnace in the position that stove connects;
2) to the driving gas with pressure of jetting in the copper smelting slag liquation in described feed tube, then in atm difference and driveThe copper smelting slag liquation in described Sheng slag container under the drive of body of taking offence is constantly risen and is flowed into described essence by described feed tubeIn furnace, then the copper smelting slag liquation in described refining furnace is constantly flowed out by described refining furnace by described drain pipe againBe back in described Sheng slag container, between described Sheng slag container, feed tube, refining furnace and drain pipe, form copper and smeltCirculating of slag liquation;
Meanwhile, in described refining furnace, the copper smelting slag liquation in described refining furnace blows oxygen-containing gas;
Utilize oxygen element in oxygen-containing gas by impurity element oxygen included in the copper smelting slag liquation in described refining furnaceChange into the oxide of corresponding impurity element, the oxide of the impurity element that oxidation forms becomes gaseous oxygen under vacuum environmentCompound volatilization removes, and realizes the process that removes impurity element in copper smelting slag;
Then the gas that is mixed with the oxide of the impurity element of gaseous state enters the condenser being communicated with described refining furnace by coldSolidifying, obtain the oxide mixture of the impurity element of condensed condensed state, realize and reclaim impurity element in copper smelting slagProcess;
Described impurity element comprise in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;
Utilize the oxidation of the oxygen element in oxygen-containing gas by the oxidation of copper smelting slag liquation, make the copper smelting slag after oxidationLiquation comprises bloodstone, cupric oxide ore and quartz mine, realizes the process of copper smelting slag oxidation;
3) described step 2) carry out after a period of time, sample examination removing impurities and oxidation after copper smelting slag liquation component andFirst content, if result of laboratory test reaches target design requirement, abolish the vacuum state in described refining furnace, then will establishFeed tube and the drain pipe put on described refining furnace diapire depart from the copper smelting slag liquation in described Sheng slag container, removing impurities oxygenChanging processing finishes; If the designing requirement of result of laboratory test miss the mark, continues removing impurities oxidation processes, until result of laboratory test reachesTarget design requirement;
Removing impurities oxidation processes finishes to obtain the oxide of the impurity element of copper smelting slag liquation after removing impurities and oxidation, condensed stateMixture and the flue gas of being discharged by described vavuum pump;
4) by step 3) first copper smelting slag liquation after the removing impurities that obtains and oxidation pass through slow cooling processing, then will pass throughThe copper smelting slag of slow cooling processing first carries out active flotation, obtains copper concentrate and active flotation mine tailing, then to described active flotationMine tailing carries out flotation and magnetic separation, obtains bloodstone, finally the mine tailing reclaiming after bloodstone is filtered, and obtains siliceous productProduct, realize the process that reclaims iron, copper and element silicon in copper smelting slag.
Preferably, described step 2) in, the mode that described oxygen-containing gas is blowed with submergence blows in described refining furnaceBelow the upper liquid level of copper smelting slag liquation, the gas outlet that sprays described oxygen-containing gas is positioned at the copper smelting slag of described refining furnaceBelow the upper liquid level of liquation.
Preferably, described step 2) in, described oxygen-containing gas is blowed to described essence in the mode of top-blown gas by oxygen rifleIn copper smelting slag liquation in furnace, the gas outlet of described oxygen rifle is positioned at the upper liquid of the copper smelting slag liquation of described refining furnaceFace above and with the upper liquid level of copper smelting slag liquation in a distance;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and contain for delivery of describedThe oxygen-containing gas passage of carrier of oxygen, described oxygen-containing gas passage is communicated with the compressed air source unit of described oxygen-containing gas;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle also comprises for improving described oxygen-containing gas spouting velocity and controlling described oxygen-containing gas injection directionShower nozzle, described shower nozzle is arranged on the bottom of described oxygen rifle, and the gas outlet of described oxygen rifle is arranged on described shower nozzle;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
Preferably, described step 2) in, when the cavity in described refining furnace is during in vacuum state, by oxygen rifle with top blastThe mode of gas is to jet in described refining furnace fuel gas and oxygen-containing gas, by described fuel gas and described oxygen-containing gasIgnition combustion, the combustion reaction liberated heat that utilizes described fuel gas and described oxygen-containing gas is in described refining furnaceCopper smelting slag liquation carries out supplementary heating processing, utilizes the combustion reaction of described fuel gas and described oxygen-containing gas to emitThe dross thing of heat cooling rear formation of copper smelting slag liquation on described refining furnace inwall to splash is removed processing;
The gas outlet of described oxygen rifle is positioned at above and and the copper smelting slag of the upper liquid level of copper smelting slag liquation of described refining furnaceThe upper liquid level of liquation in a distance;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and for delivery of described canThe fuel gas passage of combustion gas body, described fuel gas passage is communicated with the compressed air source unit of described fuel gas;
Described oxygen rifle also comprises by the sky between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent twoThat chamber forms and for delivery of the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage and described oxygen-containing gasCompressed air source unit be communicated with;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
Preferably, when the cavity in described refining furnace is during in atmospheric pressure state, by oxygen rifle with the mode of top-blown gas toWinding-up fuel gas and oxygen-containing gas in described refining furnace, by described fuel gas and described oxygen-containing gas ignition combustion, profitWith the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas to splash on described refining furnace inwallThe dross thing of the cooling rear formation of copper smelting slag liquation melts to remove to be processed, and utilizes described fuel gas and described oxygenousThe combustion reaction liberated heat of body carries out baker processing to described refining furnace;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and for delivery of described canThe fuel gas passage of combustion gas body, described fuel gas passage is communicated with the compressed air source unit of described fuel gas;
Described oxygen rifle also comprises by the sky between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent twoThat chamber forms and for delivery of the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage and described oxygen-containing gasCompressed air source unit be communicated with;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
Preferably, described step 1) in, the copper grade of described copper smelting slag liquation is less than or equal to 3%.
Compared with prior art, the invention provides a kind of resource recycle method of high impurity copper metallurgical slag, the method toolThere is following useful technique effect:
1. the present invention is directed to the direct refined copper metallurgical slag of vacuum distillation liquation, the impurity element in copper smelting slag remove speedAll very undesirable problems of rate and removal effect, have proposed improved technique scheme: in vacuum distillation process to described essenceCopper smelting slag liquation in furnace blows oxygen-containing gas, utilizes oxygen element in oxygen-containing gas by the copper smelting in described refining furnaceIn refining slag liquation, included impurity element is oxidized to the oxide of corresponding impurity element, by impurity element from complicated ore depositThing frees in mutually, the oxide of the corresponding impurity element of output, and the oxide of this impurity element can independently exist,The oxide of impurity element that oxidation forms becomes the volatilization of gaseous oxygen compound and removes under vacuum environment, in volatilization process notBe subject to again the obstruction of other material in copper smelting slag liquation, can rely on the boiling characteristics volatilization itself having, and instituteState impurity element comprise in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all, above-mentioned impurity elementOxide all has lower boiling point, and under vacuum environment, volatility is fine, has higher speed and the removal effect of removing,Some combination above, has realized the process that removes impurity element in copper smelting slag.
2. in the present invention, in described refining furnace, the copper smelting slag liquation in described refining furnace blows oxygen-containing gas,Utilize the oxygen element in oxygen-containing gas that included impurity element in the copper smelting slag liquation in described refining furnace is oxidized toThe oxide of corresponding impurity element, the oxide of the impurity element that oxidation forms becomes gaseous oxygen compound under vacuum environmentVolatilization removes, and the gas that is then mixed with the oxide of the impurity element of gaseous state enters the condenser being communicated with described refining furnaceBe condensed, obtain the oxide mixture of the impurity element of condensed condensed state, because the fusing point of oxide is than simple substanceFusing point is much higher, and the air-flow that carries a large amount of oxides is entered after condenser, and this oxide is directly condensed into substantiallyOn there is no solid granulates or the powder of adhesive, this solid granulates or powder are cooled further in dropping process, extremelyBehind condenser bottom, thoroughly lose adhesive, obtain a pile loose, the oxide particle or the oxidation that are similar to the tiny grains of sandThing powder, this oxide particle or oxide powder are above-mentioned oxide mixture. Apparently, loose,The oxide particle or the oxide powder that are similar to the tiny grains of sand can transport easily from condenser, time saving and energy saving,Thoroughly solved the problem that multicomponent alloy that above-mentioned volume is too large is difficult to transport from condenser; And this oxide mixture originallyBody is exactly graininess or Powdered, tears down pulverizing without follow-up again, time saving and energy saving, has thoroughly solved above-mentioned many simultaneouslyUnit's alloy is difficult to because quality is softer pulverize as graininess or Powdered, thereby has improved the work effect of refining removing impurities operationRate, has ensured that whole copper smelts the normal rhythm of production of flow process.
3. compared with prior art, the present invention taking temperature at the hot copper smelting slag of 1000 DEG C～1350 DEG C as handling object,First utilize oxygen to be oxidized slag, then carry out slow cooling processing, finally mainly realize copper, iron and two by technique of preparingThe separation of silica. The present invention has carried out pretreating process to described hot copper smelting slag, comprises oxidation and slow cooling two parts.Oxidizing process of the present invention makes full use of the sensible heat energy of hot melt copper smelting slag, under the oxidation of oxygen, copper is smeltedDelafossite thing in slag is oxidized, copper iron fully separates in conjunction with mineral. Along with holding of hot melt copper smelting slag slag oxidation reactionContinuous carrying out, the fayalite (2FeOSiO in copper smelting slag2) be converted into Fe3O4And SiO2, the magnetic iron ore in slag, brown ironOre deposit and pyrites are converted into Fe2O3; In the time of peroxidating, the Fe being transformed by fayalite3O4Further be oxidized to Fe2O3。And the copper sulfide minerals such as a small amount of matte in slag also can be oxidized to CuO and SiO2, metallic copper is oxidized to cupric oxide.Finally, the present invention makes iron mineral unification in copper smelting slag be converted into the bloodstone of easy choosing by oxidation, and copper mineral unification turnsTurning to can active flotation or the cupric oxide ore of leaching. After oxidation, the present invention is by carrying out the retarded cooling process of copper smelting slagMineral enrichment crystallization, for ore dressing etc. recycles ready. In the present invention, hot melt copper smelting slag is through above-mentioned pre-placeAfter reason, substantially with bloodstone (Fe2O3) and cupric oxide ore (CuO) and quartz (SiO2) mineral forms exist; Red ironReclaim by flotation and magnetic separation in ore deposit, and cupric oxide can be activated and be carried out flotation recovery by vulcanized sodium, after last tailing filtrationReclaim as quartz mineral. The present invention adopts oxidation and retarded cooling process to carry out the pretreatment of hot melt copper smelting slag, takes full advantage ofThe sensible heat resource of copper smelting slag self, by hot melt copper smelting slag is fully oxidized, is all oxidized copper mineral, iron mineralAnd copper iron separates in conjunction with mineral oxidations, making each copper mineral inversion of phases is that cupric oxide phase, each iron mineral inversion of phases are bloodstoneThing phase; Grow up by retarded cooling process enrichment and promotion mineral grain, be beneficial to following adopted ore dressing treatment process and reclaim copper, ironAnd silicon. Therefore, method flow provided by the invention is short, technique simple, be easy to realization and control, has substantially met copper smeltingThe demand of the copper smelting slag recycling treatment of refining industry, has the advantages such as the scope of application is wide and practical. In addition, thisThe bright method that reclaims copper, iron and silicon from copper smelting slag providing does not produce secondary refuse, pollution-free, has saved a large amount of energyThe input in source.
Brief description of the drawings
Fig. 1 is the operation principle schematic diagram of the resource recycle method of high impurity copper metallurgical slag provided by the invention.
In figure: 1 refining furnace, 2 feed tubes, 201 driving gas pipes, 3 drain pipes, 4 oxygen rifles, 5 contain slag container.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawing in the present invention, to thisTechnical scheme in invention is clearly and completely described, and obviously, described embodiment is that a part of the present invention is realExecute example, instead of whole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art are not makingThe every other embodiment obtaining under the prerequisite of creative work, belongs to the scope of protection of the invention.
In description of the invention, it will be appreciated that term " " center ", " axially ", " radially ", " longitudinally ", " horizontal strokeTo ", " length ", " width ", " on ", D score, 'fornt', 'back', " left side ", " right side ", " top ", " end ", " interior ", " outside "," clockwise ", " counterclockwise ", " level ", " vertically " etc. instruction orientation or position relationship be based on shown in accompanying drawing or realityOrientation or position relationship in the application of border, be only the present invention for convenience of description and simplified characterization, instead of instruction or hintThe device of indication or element must have specific orientation, construct and operation with specific orientation, and it is right therefore can not to be interpreted asRestriction of the present invention.
According to above-mentioned analysis conclusion, the invention provides a kind of resource recycle method of high impurity copper metallurgical slag, comprise withLower step:
1) the copper smelting slag liquation of melting is joined to the Sheng slag container 5 for splendid attire copper smelting slag liquation; Then willThe feed tube 2 and the drain pipe 3 that are arranged on refining furnace 1 diapire are immersed in the upper liquid of containing slag container 5 interior copper smelting slag liquationsThe following certain depth of face, then opens the vavuum pump that is communicated with refining furnace 1 by the state that is evacuated of the cavity in refining furnace 1,Now under the effect of the atm difference between the interior vacuum residual voltage of refining furnace 1 and external atmosphere pressure, contain the copper smelting in slag container 5Refining slag liquation rises and flows in the cavity of refining furnace 1 along the cavity passage in feed tube 2 and drain pipe 3;
The profile of refining furnace 1 is vertical column, and inner hollow forms cavity, and refining furnace 1 comprises steel shell and builds by laying bricks or stonesAt the refractory lining of steel shell inner surface, the top of refining furnace 1 is provided with the gas outlet for being connected with vavuum pump;
Feed tube 2 includes steel inner casing with drain pipe 3, be arranged on steel inner casing inner surface refractory lining withAnd be arranged on the refractory material outer lining of the outer surface of steel inner casing;
Feed tube 2 and drain pipe 3 are fixedly installed on the diapire of refining furnace 1 and are tightly connected with the diapire of refining furnace 1,Cavity passage in cavity in refining furnace 1 and feed tube 2 is interconnected, in the cavity in refining furnace 1 and drain pipe 3Cavity passage be interconnected, all devices that are connected with refining furnace 1 all seal at the position being connected with refining furnace 1Process to prevent from destroying the vacuum state in refining furnace 1;
2) to the driving gas with pressure of jetting in the copper smelting slag liquation in feed tube 2, then in atm difference and drivingThe copper smelting slag liquation of containing under the drive of gas in slag container 5 is constantly risen and is flowed in refining furnace 1, so by feed tube 2Copper smelting slag liquation in rear refining furnace 1 is constantly flowed out to be back to by refining furnace 1 by drain pipe 3 again contains slag container 5In, containing the circular flow that forms copper smelting slag liquation between slag container 5, feed tube 2, refining furnace 1 and drain pipe 3Moving;
Meanwhile, in refining furnace 1, the copper smelting slag liquation in refining furnace 1 blows oxygen-containing gas;
Utilize the oxygen element in oxygen-containing gas that included impurity element in the copper smelting slag liquation in refining furnace 1 is oxidized toThe oxide of corresponding impurity element, the oxide of the impurity element that oxidation forms becomes gaseous oxygen compound under vacuum environmentVolatilization removes, and realizes the process that removes impurity element in copper smelting slag;
Then the gas that is mixed with the oxide of the impurity element of gaseous state enters the condenser being communicated with refining furnace 1 and is condensed,Obtain the oxide mixture of the impurity element of condensed condensed state, realize the mistake that reclaims impurity element in copper smelting slagJourney;
Impurity element comprise in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;
Utilize the oxidation of the oxygen element in oxygen-containing gas by the oxidation of copper smelting slag liquation, make the copper smelting slag after oxidationLiquation comprises bloodstone, cupric oxide ore and quartz mine, realizes the process of copper smelting slag oxidation;
3) step 2) carry out after a period of time, component and the content of the copper smelting slag liquation after sample examination removing impurities and oxidation,If result of laboratory test reaches target design requirement, first abolish the vacuum state in refining furnace 1, then will be arranged on refiningFeed tube 2 on stove 1 diapire and drain pipe 3 depart from the copper smelting slag liquation of containing in slag container 5, removing impurities oxidation processes knotBundle; If the designing requirement of result of laboratory test miss the mark, continues removing impurities oxidation processes, until result of laboratory test reaches target designRequirement;
Removing impurities oxidation processes finishes to obtain the oxide of the impurity element of copper smelting slag liquation after removing impurities and oxidation, condensed stateMixture and the flue gas of being discharged by vavuum pump;
4) by step 3) first copper smelting slag liquation after the removing impurities that obtains and oxidation pass through slow cooling processing, then will pass throughThe copper smelting slag of slow cooling processing first carries out active flotation, obtains copper concentrate and active flotation mine tailing, then to described active flotationMine tailing carries out flotation and magnetic separation, obtains bloodstone, finally the mine tailing reclaiming after bloodstone is filtered, and obtains siliceous productProduct, realize the process that reclaims iron, copper and element silicon in copper smelting slag.
Utilize the principle of vacuum distillation to carry out the method for refining removing impurities, had in the prior art a lot. But, existingIn technology, normally multicomponent alloy of the handled object of vacuum distillation refining removing impurities, element volatilizees mainly with metal simple-substance state.And in the present invention pending to as if copper smelting slag, be a kind of slag, if this copper smelting slag is placed directly in to vacuum environmentUnder carry out vacuum distillation refining removing impurities, impurity element remove speed and removal effect is all very undesirable. Reason is: many institutesKnown, slag is a kind of very complicated thing phase, is a kind of mineral facies, and impurity element wherein does not exist independent phase substantially,But be easy to form mineral facies with other host element, for example: form the copper mineral phase and the iron that contain a large amount of impurity elementsMineral facies, in the time of vacuum distillatory refining, these mineral facies can seriously hinder the volatilization of its contained impurity element, thereby seriousGround has affected rate of volatilization and the volatility of impurity element. For this reason, the present invention proposes improved technique scheme: steam in vacuumHeat up in a steamer in process to the copper smelting slag liquation in refining furnace 1 and blow oxygen-containing gas, utilize oxygen element in oxygen-containing gas by refiningIn copper smelting slag liquation in stove 1, included impurity element is oxidized to the oxide of corresponding impurity element, by impurity unitElement frees from complicated mineral facies, the oxide of the corresponding impurity element of output, the oxide energy of this impurity elementEnough independent existence, the oxide of the impurity element that oxidation forms becomes the volatilization of gaseous oxygen compound and removes under vacuum environment,In volatilization process, be no longer subject to the obstruction of other material in copper smelting slag liquation, can rely on the volatilization spy who itself hasProperty volatilization, and impurity element comprise in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all, above-mentioned assortedThe oxide of prime element all has lower boiling point, and under vacuum environment, volatility is fine, have higher remove speed andRemoval effect, above some combination, has realized the process that removes impurity element in copper smelting slag.
In vacuum distillation refining removing impurities process now, above-mentioned lead impurity element, zinc, arsenic, antimony, bismuth and/or tin elementMainly directly volatilize with simple substance form, secondly directly volatilize with oxide morphology. Above-mentioned simple substance and sulfide become gas and waveSend out and enter after the free space on refining furnace 1 top, because the temperature in the free space on refining furnace 1 top is higher, and byIn the at high temperature unstable easy generation thermal decomposition of sulfide of lead, zinc, arsenic, antimony, bismuth and/or tin element, make above-mentionedSulfide the overwhelming majority correspondingly thermal decomposition be simple substance lead, zinc, arsenic, antimony, bismuth and/or tin and elemental sulfur, thenThermal decomposition produce simple substance lead, zinc, arsenic, antimony, bismuth and/or tin, elemental sulfur and volatilize with simple substance form at the very startSimple substance lead, zinc, arsenic, antimony, bismuth and/or tin enter follow-up condenser condenses with one, air-flow, due to elemental sulfurFusing point and boiling point are all lower, conventionally can condensation in condenser, but continue to flow into follow-up device with gaseous state, thereforeCommon only above-mentioned simple substance lead, zinc, arsenic, antimony, bismuth and/or the tin of condensation in condenser. Due to simple substance lead, zinc, arsenic,The fusing point of antimony, bismuth and/or tin is lower, and further, simple substance lead, zinc, arsenic, antimony, bismuth and/or tin in condensation processBlending mutually, forms the multicomponent alloy that comprises lead, zinc, arsenic, antimony, bismuth and/or tin element, the fusing point of this multicomponent alloyLower, all lower than any one fusing point in Element Lead, zinc, arsenic, antimony, bismuth and tin, though multicomponent alloy is condensed,But normally liquid after condensation, be semi liquid state semisolid at the most, substantially can formation not there is the solid-state of adhesive, makeObtain condensed multicomponent alloy and still there is mobility and adhesive, the droplet of multicomponent alloy or semi liquid state semisolidAnd the granule with very strong adhesive finally comes together in the bottom of condenser, is further condensed, and is finally easy to condensationForm very large one the sticking together greatly or a bulk of solid-state multicomponent alloy of volume, because volume is too large, this solid-state multicomponent alloy is difficult toFrom the former the design's of condenser material outlet, transport, need first by condenser shut down, then wait for condenser insideTemperature is down to and is approached room temperature, then opens condenser, allows workman enter condenser and tears down bulk, wastes time and energy; AndBecause volume is too large, even after this solid-state multicomponent alloy transports from condenser, also must it be torn down and be pulverized with sideJust subsequent treatment, wastes time and energy, and due to the hardness of the metal simple-substance of lead, zinc, arsenic, antimony, bismuth and/or tin elementLow, make above-mentioned multicomponent alloy quality softer, be therefore difficult to this bulk multicomponent alloy to be ground into graininess or Powdered.To sum up, current technique makes to become the impurity element that gaseous volatilization removes and is condensed in condenser with simple substance form, veryEasily form the very large a bulk of multicomponent alloy of volume, this multicomponent alloy, due to reasons such as volume are too large, quality is softer, is givenFollow-up processing brings a lot of negative influences, has seriously reduced the operating efficiency of refining removing impurities operation, has had a strong impact on wholeIndividual copper is smelted the normal rhythm of production of flow process. For this reason, in the present invention, step 2) in, in refining furnace 1, to refining furnaceCopper smelting slag liquation in 1 blows oxygen-containing gas, utilizes oxygen element in oxygen-containing gas by the copper smelting slag in refining furnace 1In liquation, included impurity element is oxidized to the oxide of corresponding impurity element, the oxidation of the impurity element that oxidation formsThing becomes the volatilization of gaseous oxygen compound and removes under vacuum environment; Then be mixed with the gas of the oxide of the impurity element of gaseous stateEnter the condenser being communicated with refining furnace 1 and be condensed, obtain the oxide mixture of the impurity element of condensed condensed state,Realize the process that reclaims impurity element in copper smelting slag; Because the fusing point of oxide is more much higher than the fusing point of simple substance, makeThe air-flow that carries a large amount of oxides enters after condenser, and this oxide is directly condensed into and there is no the solid-state of adhesiveParticle or powder, this solid granulates or powder are cooled further in dropping process, to condenser bottom, thoroughly loseGo adhesive, obtain a pile loose, the oxide particle or the oxide powder that are similar to the tiny grains of sand, this oxideGrain or oxide powder are above-mentioned oxide mixture. Apparently, oxygen loose, that be similar to the tiny grains of sandCompound particle or oxide powder transport easily from condenser, time saving and energy saving, have thoroughly solved above-mentioned volume too largeThe multicomponent alloy problem that is difficult to transport from condenser; And this oxide mixture itself is exactly graininess or Powdered,Tear down again pulverizing without follow-up, time saving and energy saving, thoroughly solve above-mentioned multicomponent alloy and be difficult to because quality is softer simultaneouslyPulverizing is graininess or Powdered, thereby has improved the operating efficiency of refining removing impurities operation, has ensured whole copper smelting flow processNormal rhythm of production.
In the present invention, it is only lead impurity element, zinc, arsenic, antimony, the bismuth removing in copper smelting slag liquation that refining removing impurities is processedAnd/or tin element, do not change the proterties of copper smelting slag liquation; Oxidation processes is only by the each iron ore in copper smelting slagThing is oxidized to bloodstone, and the each copper mineral in copper smelting slag liquation is oxidized to cupric oxide ore, makes oxygen-containing gas oxidationAfter copper smelting slag liquation comprise bloodstone, cupric oxide ore and quartz mine, be only to change the thing phase state of contained element; OnState step 3) in " removing impurities oxidation processes finishes to obtain the copper smelting slag liquation after removing impurities and oxidation " " removing impurities and oxygen of mentioningCopper smelting slag liquation after change " remain copper smelting slag liquation, be the copper smelting slag liquation that has removed part of impurity elements,That thing phase state has obtained the copper smelting slag liquation changing.
In the present invention, above-mentioned oxygen-containing gas is preferably air or oxygen-enriched air, and in oxygen-enriched air, the percent by volume of oxygen is25%～95%. Preferably, with oxygen stoichiometry, the amount of blowing of controlling oxygen is 7m3/ t slag～10m3/ t slag.
In the present invention, for the target design requirement of result of laboratory test, apparently, lead, zinc, arsenic, antimony, bismuth and tinThe volatility of these six kinds of elements varies, and these six kinds of elements are unlikely removed to ideal value simultaneously, therefore, and above-mentioned orderMark designing requirement can only be using the content of the some elements in element in above-mentioned 6 or certain several element as target reference, onlyCan be using the content of the some elements to Influence of production maximum or certain several element for example, as target reference: plumbous and arsenic twoKind of element content in copper concentrate is the highest, and the two is to having the greatest impact of producing, therefore can be with plumbous and these two kinds of elements of arsenicContent is as the target design requirement of above-mentioned result of laboratory test, as long as the lead of sample examination and the content of arsenic have reached target designRequirement, just means that removing impurities process finishes, and first abolishes the vacuum state in refining furnace 1; As for all the other impurity elementsRemoval effect whether reach desired level, do not do to go into seriously. Can also containing with cupric oxide ore in copper smelting slag or bloodstoneWhether amount reaches the target design requirement of ideal value as above-mentioned result of laboratory test.
In the present invention, above-mentioned driving gas is nitrogen or argon gas, is preferably nitrogen.
In the present invention, above-mentioned vacuum residual voltage refers to the pressure of refining furnace 1 internal cavity remaining gas under vacuum state,The same with the meaning of noun vacuum. Preferably, step 2) in vacuum residual voltage be 100Pa～1000Pa.
In the present invention, structure and the type of the Sheng slag container 5 for splendid attire copper smelting slag liquation are not restricted, meet and useIn this function of splendid attire copper smelting slag liquation, these Sheng slag container 5 end faces at least have an opening to allow refining furnace1 oscilaltion.
In the present invention, by being arranged on driving gas pipe 201 on feed tube 2 to the copper smelting slag liquation in feed tube 2Middle winding-up driving gas with pressure.
In the present invention, it is higher that high impurity copper concentrate means in copper concentrate the content of impurity element, impurity element comprise lead, zinc,One or more in arsenic, antimony, bismuth and tin element or whole, the content exceed industry of impurity element is general to its contentClaimed range. In the present invention, in actual production, above-mentioned copper concentrate not necessarily comprises whole above-mentioned six kinds of impurity elements,May comprise and one or more of above-mentioned six kinds of impurity elements also may comprise whole above-mentioned six kinds of elements. Actual productionIn, even if above-mentioned copper concentrate comprises a certain of six kinds of above-mentioned impurity elements, but the content of this impurity element may be not yetThe exceed industry universal standard, but the content exceed industry universal standard of other contained certain impurity element. Actual productionIn, as long as contained impurity element is that one of above-mentioned six kinds of impurity elements and this impurity content exceed in above-mentioned copper concentrateIndustry universal standard, this copper concentrate is just high impurity copper concentrate. High impurity copper concentrate is through the smelting slag one of melting operation outputAs be exactly high impurity smelting slag.
The percentage by weight of above-mentioned six kinds of impurity elements that may exist in the accessible high impurity copper metallurgical slag of the present inventionPreferred higher limit is: plumbous≤5.0%, zinc≤10.0%, arsenic≤5.0%, antimony≤3.0%, bismuth≤5.0%, tin≤1.0%.
The invention provides a kind of resource recycle method of high impurity copper metallurgical slag, apparently, this resource reclaimsMethod is not to process high impurity copper metallurgical slag, processes the crowd that high impurity copper metallurgical slag is only this resource recycle methodIn multi-functional relatively outstanding a bit; Since this resource recycle method can be processed high impurity copper metallurgical slag, obviously,It also can the normal copper smelting slag of processing element content. Adopt resource recycle method processing element provided by the invention to containMeasure normal copper smelting slag also in protection scope of the present invention. As long as adopt resource recycle method provided by the inventionProcess copper smelting slag, all in protection scope of the present invention.
The principle that in the present invention, copper smelting slag liquation circulates: when by feed tube 2 Hes that are arranged on refining furnace 1 bottom surfaceDrain pipe 3 is immersed in the following certain depth of upper liquid level of containing slag container 5 inner melts, and then unlatching is communicated with refining furnace 1Vavuum pump is the state that is evacuated of the cavity in refining furnace 1, now the interior vacuum residual voltage of refining furnace 1 and external atmosphere pressure itBetween the effect of atm difference under the liquation contained in slag container 5 rise and flow into along the cavity passage of feed tube 2 and drain pipe 3In the cavity of refining furnace 1; Copper smelting slag liquation now does not circulate; For copper smelting slag liquation is circulated,To the driving gas with pressure of jetting in the liquation in feed tube 2, driving gas enters after the liquation in feed tube 2 owing to being subject toThermal expansion and pressure drop, cause isothermal expansion, produce a large amount of nuclei of bubbles and expand rapidly in interior moment of feed tube 2,The gas-powered copper smelting slag liquation expanding rises, and contains melting in slag container 5 under the drive of atm difference and driving gasLiquid is constantly risen and is flowed in refining furnace 1 by feed tube 2, and then the liquation in refining furnace 1 is continuous by drain pipe 3 againGround is flowed out to be back to by refining furnace 1 to be contained in slag container 5, is containing slag container 5, feed tube 2, refining furnace 1 and fluidBetween pipe 3, form circulating of liquation.
In the present invention, this that above-mentioned lead impurity element, zinc, arsenic, antimony, bismuth and/or tin element volatilize with oxide formIndividual process mainly occurs in the upper surface vicinity of containing the copper smelting slag liquation in slag container 5, when showing on copper smelting slag liquationAfter near impurity element face is removed, is positioned at copper smelting slag liquation impurity element inner and bottom and relies on diffusion power to be openedThe near surface place diffusion of beginning upwards, recovers to improve the impurity content of copper smelting slag liquation upper surface vicinity, makes thisThe impurity element at place enters the state that removes of volatilization of waiting for, obviously, contain slag container 5, feed tube 2, refining furnace 1 withAnd between drain pipe 3, forming circulating of liquation, liquation big cycle volume like this ground flows for removing in copper smelting slag liquationAbove-mentioned impurity element improved very favourable dynamic conditions, the mobile of big cycle volume improved in copper smelting slag liquationThe impurity element of portion and bottom diffuses to the speed of liquid level vicinity, has reduced diffusion time, also makes copper smelting slag moltenLiquid impurity element inner and bottom can rise to the upper liquid level vicinity of copper smelting slag liquation substantially, thereby improvesRemoving impurities speed and the removing impurities degree of refining removing impurities processing, the removing impurities cycle of having reduced the processing of refining removing impurities.
In the present invention, the temperature of copper smelting slag is at 1000 DEG C～1350 DEG C, preferably within the scope of 1100 DEG C～1250 DEG C.The present invention is not particularly limited the source of hot copper smelting slag, can process copper grade and be less than or equal to 3% smelting slag, converterSlag and electric dilution slag etc., also can process a step copper slag and blowing slag that copper grade is greater than 3%.
In above-mentioned oxidizing process, the present invention makes full use of the sensible heat energy of hot slag, under the oxidation of oxygen, makesIn slag, delafossite thing is oxidized, and makes copper iron fully separate in conjunction with mineral simultaneously. Along with hot melt copper smelting slag oxidation reactionContinue to carry out the fayalite (2FeOSiO in copper smelting slag2) be converted into Fe3O4And SiO2, magnetic iron ore in slag, brownIron ore and pyrites are converted into Fe2O3; In the time of peroxidating, the Fe being transformed by fayalite3O4Further be oxidized to Fe2O3。And the copper sulfide minerals such as a small amount of matte in slag also can be oxidized to CuO and SiO2, metallic copper is oxidized to cupric oxide.Finally, the present invention by oxidation make iron mineral unification in slag be converted into easy choosing bloodstone, copper mineral unification is converted into canWith the cupric oxide ore of active flotation or leaching.
Utilize the oxidation of the oxygen element in oxygen-containing gas by the fayalite oxidation Decomposition in copper smelting slag liquation to beFe3O4And SiO2And be independent iron mineral and independent copper mineral by iron copper in conjunction with mineral oxidation Decomposition, and control oxygenousThe quantity delivered of the body the most at last ferro element in copper smelting slag liquation is oxidized to Fe2O3To make the various iron ores in copper smelting slagThing is oxidized to bloodstone, and the copper in copper smelting slag liquation is oxidized to cupric oxide to make in copper smelting slag liquationVarious copper minerals are oxidized to cupric oxide ore, the copper smelting slag liquation after oxygen-containing gas oxidation comprise bloodstone, cupric oxide ore andQuartz mine, realizes the process of copper smelting slag oxidation.
After the oxidation of certain hour, the copper smelting slag that the present invention obtains oxidation carries out slow cooling processing. The present invention passes through slagRetarded cooling process carry out mineral enrichment crystallization, for the recycling such as ore dressing ready. In one embodiment of the invention,Slow cooling is processed and is comprised successively: natural slow cooling 24 hours and add water cooling 36 hours. Wherein, adding water cooling can adopt and addThe mode of water spray is carried out.
The present invention adopts oxidation and retarded cooling process to carry out hot slag pretreatment, takes full advantage of the sensible heat money of copper smelting slag selfSource, by hot melt copper smelting slag aerobic oxidation, is all oxidized copper mineral, iron mineral and copper iron is divided in conjunction with mineralFrom, making each copper mineral inversion of phases is that cupric oxide phase, each iron mineral inversion of phases are bloodstone thing phase; Then pass through retarded cooling processEnrichment and promotion mineral grain are grown up. In the present invention, hot melt copper smelting slag is after above-mentioned pretreatment, substantially with redIron ore (Fe2O3) and cupric oxide ore (CuO) and quartz (SiO2) mineral forms exist, obtain through slow cooling processingCopper smelting slag, has strengthened the washability of various resource mineral in slag, is beneficial to following adopted ore dressing treatment process and reclaims copper, ironAnd silicon.
After slow cooling is processed, before ore dressing is processed, the present invention preferably also comprises: will carry out through the copper smelting slag of slow cooling processingGrinding. Grinding is technological means well known to those skilled in the art, in an embodiment of the present invention, and copper smelting slag after grindingFineness be 85 order～325 orders, be preferably 100 order～300 orders. After slow cooling processing finishes, the present invention can will contain slagSlag in container 5 is poured out, and with sending into ore grinding-ore-sorting system by belt after crusher in crushing, slag is through grinding millOre deposit, become the ore pulp of certain fineness laggard enter ore-sorting system.
The present invention, by first carrying out active flotation through the copper smelting slag of slow cooling processing, obtains copper concentrate and active flotation mine tailing,Again described active flotation mine tailing is carried out to flotation and magnetic separation, obtain bloodstone, finally the mine tailing reclaiming after bloodstone is carried outFilter, obtain siliceous product, realize the process that reclaims iron, copper and element silicon in copper smelting slag.
In this technological process, the present invention first adopts active flotation to reclaim copper oxide mineral, obtain copper concentrate andActive flotation mine tailing. Wherein, active flotation is technological means well known to those skilled in the art. Active flotation sulfuration usedThe consumption of sodium is preferably 150g/t slag～600g/t slag, more preferably 200g/t slag～500g/t slag; Collecting usedAgent can adopt the conventional flotation medicaments such as xanthate, and its consumption is preferably 60g/t slag～300g/t slag, and more preferably 100G/t slag～200g/t slag.
Obtain after copper concentrate and active flotation mine tailing, the present invention again to active flotation mine tailing by flotation and magnetic separation, carry out ironThe comprehensive recovery of mineral. The present invention is by floating magnetic combined process flow, and comprehensive recovery of iron mineral can adopt following two kinds of techniques.A kind of technique is: obtain, after copper concentrate and active flotation mine tailing, active flotation mine tailing first being carried out to flotation, obtain major partBloodstone and flotation tailing; Again flotation tailing is carried out to magnetic separation, obtain remaining bloodstone and magnetic tailing; Finally by magnetic separationMine tailing filters, and obtains siliceous product. Another kind of technique is: obtain after copper concentrate and active flotation mine tailing, to activationFlotation tailing carries out high intensity magnetic separation and reverse flotation successively, obtains bloodstone, reverse flotation mine tailing and high intensity magnetic separation mine tailing; Finally will be anti-Flotation tailing and high intensity magnetic separation mine tailing filter after merging, and obtain siliceous product.
In these two kinds of techniques, flotation, magnetic separation, high intensity magnetic separation, reverse flotation and filtration etc. are those skilled in the art and knowTechnological means, the present invention is not particularly limited.
The present invention is directed to low-grade copper smelting slag, adopt active flotation technique to reclaim after copper mineral, adopt flotation, magnetic separationRespectively bloodstone is comprehensively reclaimed, be conducive to improve the rate of recovery of iron mineral.
The iron ore concentrate obtaining by this technique, according to purity and fineness situation, can be used as iron-smelting raw material and produces super iron essenceThe raw material of ore deposit or iron oxide red; The siliceous product silicon content and the fineness that obtain are higher, are the siliceous product of height, can be used as to smelt to joinThe construction materials such as material and making glass, cast stone and dry powder and mortar, produce market scope is very extensive; The copper concentrate that obtains,Electro deposited copper or copper smelting slag can return to copper and smelt.
To sum up, method flow provided by the invention is short, and technique is simple, be easy to realize and control, and has substantially met copper smeltingThe demand of the copper smelting slag recycling treatment of industry, has the features such as the scope of application is wide and practical strong. In addition, the present invention carriesThe method that reclaims copper, iron and silicon from copper smelting slag of confession does not produce secondary refuse, pollution-free, has saved mass energyDrop into.
Blow the mode that specifically blows of oxygen-containing gas for the copper smelting slag liquation in refining furnace 1, at one of the present inventionIn embodiment, provide one to blow mode: step 2) in, the mode that oxygen-containing gas is blowed with submergence blows to refiningBelow the upper liquid level of the copper smelting slag liquation in stove 1, the gas outlet of ejection oxygen-containing gas is positioned at the copper of refining furnace 1 and smeltsBelow the upper liquid level of slag liquation.
In one embodiment of the invention, also provide another to blow mode: step 2) in, by oxygen rifle 4In the mode of top-blown gas, oxygen-containing gas is blowed to the copper smelting slag liquation in refining furnace 1 to the position, gas outlet of oxygen rifle 4More than the upper liquid level of the copper smelting slag liquation in refining furnace 1 and with the upper liquid level of copper smelting slag liquation in a distance;Oxygen rifle 4 is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and oxygen rifle 4 comprises by the sky in hollow pipeThat cavity inside and outside chamber or adjacent two between the tube wall of the hollow pipe of suit forms and for delivery of oxygen-containing gas containing oxygenGas passage, oxygen-containing gas passage is communicated with the compressed air source unit of oxygen-containing gas; Oxygen rifle 4 also comprises by adjacent two inner-outer sleevesIt is that cavity between the tube wall of hollow pipe of dress forms and for oxygen rifle 4 being carried out to the cool cycles aquaporin of cooling protection,Cool cycles aquaporin is communicated with apparatus for supplying cool water; Oxygen rifle 4 also comprises for improving oxygen-containing gas spouting velocity and controlThe shower nozzle of oxygen-containing gas injection direction processed, shower nozzle is arranged on the bottom of oxygen rifle 4, and the gas outlet of oxygen rifle 4 is arranged on shower nozzle;Oxygen rifle 4 is arranged on the roof of refining furnace 1 and can slides up and down along the roof of refining furnace 1.
Preferably, in actual production, can adopt two kinds of above-mentioned oxygen-containing gas to blow mode simultaneously.
Oxygen-containing gas is not suitable for being blown into and containing slag appearance in the mode of top blast, side-blown and/or bottom blowing on the wall of containing slag container 5In copper smelting slag liquation in device 5, because this oxygen-containing gas is to be blown into copper to smelt liquation in the outside of refining furnace 1, depositBe that a large amount of oxygenous cognition in copper smelting slag liquation affects that copper smelting slag liquation successfully enters in vacuum stateRefining furnace 1, can affect circulating of copper smelting slag liquation, and then affects removing impurities oxid-reclamatiom effect.
Removing impurities oxid-reclamatiom process needs certain hour, and within this time period, the temperature meeting of copper smelting slag liquation can notDecline with avoiding, therefore need copper smelting slag liquation to carry out heat make-up heat. General mode of heating in industry at presentFor: the burner of several burning combustibles and oxygen-containing gas is set on the furnace wall, side of containing slag container 5 to containing slag containerCopper smelting slag liquation in 5 carries out heating and thermal insulation, burner and the upper liquid level phase of containing the copper smelting slag liquation in slag container 5Apart from certain distance, there are several problems in this mode of heating: 1. so mode of heating is similar to the pattern of " broad irrigation ",The heat that burner produces is let drift, and the heat that burner produces is not applied in the place of real needs, heat fullyAmount serious waste phenomenon, heat utilization ratio is lower; 2. the heat that burner produces is first by more than copper smelting slag liquation liquid levelHeating in space, then the heat in upper space passes to the copper smelting slag liquation of below in the mode of radiant heat transfer,In this process, heat transfer pattern has and only has this one of radiant heat transfer pattern, and according to metallurgical thermodynamics principle, radiant heat transfer mouldFormula is the one of several of heat transfer efficiency minimum in numerous heat transfer patterns, and therefore, current mode of heating exists heat utilization ratioLow and the less problem of heat transfer rate; 3. because the length and width face area of common Sheng slag container 5 is larger, only containing slag container 5Furnace wall, side on several burners are set is irrational, obviously, protect near the copper smelting slag liquation heating of burnerTemp effect is better, the copper smelting slag liquation from burner away from more, and heating and thermal insulation effect is poorer, for containing in slag container 5All copper smelting slag liquations, heating and thermal insulation effect is extremely inhomogeneous. Apparently, there is the order of above-mentioned multiple problemsBefore mode of heating, be unfavorable for solving the above-mentioned technical problem of mentioning in the present invention, be unfavorable for removing impurities oxid-reclamatiom processCarry out. For this reason, in one embodiment of the invention, in removing impurities oxid-reclamatiom process, when the cavity in refining furnace 1In the time of vacuum state, by oxygen rifle 4 in the mode of top-blown gas to the interior winding-up fuel gas of refining furnace 1 and oxygen-containing gas,By fuel gas and oxygen-containing gas ignition combustion, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas to essenceCopper smelting slag liquation in furnace 1 carries out supplementary heating processing, utilizes the combustion reaction of fuel gas and oxygen-containing gas to emitThe dross thing of heat cooling rear formation of copper smelting slag liquation on refining furnace 1 inwall to splash melt removing placeReason; It is above and with copper smelting slag liquation that the gas outlet of oxygen rifle 4 is positioned at the upper liquid level of copper smelting slag liquation of refining furnace 1Upper liquid level in a distance; Oxygen rifle 4 is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, oxygen rifle4 comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent two and forThe fuel gas passage of transporting combustible gases, fuel gas passage is communicated with the compressed air source unit of fuel gas; Oxygen rifle 4 also wrapsDraw together formed by the cavity between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent two and for defeatedSend the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage is communicated with the compressed air source unit of oxygen-containing gas; Oxygen rifle 4 also comprisesThat formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for oxygen rifle 4 being carried out to cooling protectionCool cycles aquaporin, cool cycles aquaporin is communicated with apparatus for supplying cool water; Oxygen rifle 4 is arranged on the top of refining furnace 1On wall and can slide up and down along the roof of refining furnace 1.
Preferably, fuel gas is natural gas or coal gas.
The present invention, the cavity in refining furnace 1 in the time of vacuum state, by oxygen rifle 4 in the mode of top-blown gas to essenceThe interior winding-up fuel gas of furnace 1 and oxygen-containing gas, by fuel gas and oxygen-containing gas ignition combustion, utilize fuel gas andThe combustion reaction liberated heat of oxygen-containing gas carries out supplementary heating processing to the copper smelting slag liquation in refining furnace 1, soHeating, because oxidation operation is all carried out and completes in refining furnace 1, and also all exists by the combustion heating of oxygen rifle 4In refining furnace 1, carry out, heat supplier and caloric requirement Fang Jun are in refining furnace 1, and the heat therefore producing can be wholeGround and be directly transferred to this part the copper smelting slag liquation that is oxidized operation in refining furnace 1, the heat amount of generationBefore improving, obviously reduce, but for this part the copper smelting slag liquation that is oxidized operation process in refining furnace 1Through enough, adopt a small amount of and sufficient heat only this part the copper smelting slag liquation that is oxidized operation accurately to be mendedFill, the heat of generation is all used in the place needing, and avoids the heating mode of original " broad irrigation ", inexcessive, noWaste, has improved heat utilization ratio, has reduced the consumption of combustible and oxygen-containing gas; Unnecessary heat can be along with copper smeltingThe big cycle volume of refining slag liquation flows and is delivered to refining furnace 1 in refining furnace 1, passes to and contains slag container 5 all the other positionsCopper smelting slag liquation, enter before being oxidized operation entering refining furnace 1 containing copper smelting slag liquation in slag container 5Row preheating insulation, big cycle volume flowing heat transfer belongs to convection heat transfer' heat-transfer by convection in metallurgical thermodynamics, the heat transfer efficiency phase of convection heat transfer' heat-transfer by convectionRatio is much higher in radiant heat transfer, and therefore the present invention is except the lower heat transfer pattern of this heat transfer efficiency of radiant heat transfer, alsoThere is the heat transfer pattern that this heat transfer efficiency of convection heat transfer' heat-transfer by convection is higher, thereby improved significantly the biography of mode of heating of the present inventionThe thermal efficiency; Because the present invention only directly carries out this part the copper smelting slag liquation that is oxidized operation in refining furnace 1, apparently, can there is not the inhomogeneous phenomenon of above-mentioned heating in heating and thermal insulation. To sum up, mode of heating of the present inventionThe requirement of the copper smelting slag liquation that has ensured to carry out removing impurities oxidation operation to temperature, has improved the speed of carrying out of removing impurities oxidation operationDegree and performance level.
Copper smelting slag liquation doped with driving gas enters after the vacuum environment in refining furnace 1, and at the extraneous oxygen that contains of re-blowingIn the situation of gas, the copper smelting slag liquation in refining furnace 1 can not be to circulate imperturbably, but violent splash,So, inevitably with regard to some copper smelting slag liquation splash to the inwall of refining furnace 1, due to refining furnace 1The temperature of upper space and upper inside wall is lower, liquid copper smelting slag liquation meeting cooled and solidified, in the course of time, just in essenceThe inner wall surface of furnace 1 forms the hard dross thing of one deck. Apparently, this cold conditions dross thing is to removing impurities oxid-reclamatiomProcess and for example, to all there is no positive role the service life of refining furnace 1: due to dross thing contain higher lead,The elements such as zinc, arsenic, antimony, bismuth, after removing impurities oxid-reclamatiom finishes, this dross thing can cause reached target component wantThe copper smelting slag liquation of asking returns lead, Hui Xin, returns arsenic etc., causes lead, zinc or arsenic element in copper smelting slag liquation again to riseHigh; Dross thing can corrode the refractory lining of refining furnace 1; Dross thing also can reduce the dischargeable capacity of refining furnace 1. ForThis, in the present embodiment, in removing impurities oxid-reclamatiom process, when the cavity in refining furnace 1 is during in vacuum state, pass throughOxygen rifle 4 in the mode of top-blown gas to the interior winding-up fuel gas of refining furnace 1 and oxygen-containing gas, by fuel gas and oxygenousBody ignition combustion, the combustion reaction liberated heat that utilizes fuel gas and oxygen-containing gas to splash on refining furnace 1 inwallThe dross thing of the cooling rear formation of copper smelting slag liquation remove processing, improve in refining furnace 1 internal upper part space and topThe temperature of wall prevents that the copper smelting slag liquation cooled and solidified of splash from forming dross thing, thereby reduces the generation that finishes effluent; CarryThe temperature of high refining furnace 1 internal upper part space and upper inside wall makes dross thing melted by heat again become liquid, along refiningThe inwall of stove 1 flows downward, and is again back in the copper smelting slag liquation circulating, and completes removing impurities oxid-reclamatiom process,Thereby reduce the quantity of the dross thing having generated, thereby weakened a series of passive shadow that above-mentioned dross thing bringsRing.
At present, no matter how to optimize refinery practice in removing impurities oxid-reclamatiom process, after removing impurities oxid-reclamatiom finishes, refiningStill can remaining a certain amount of dross thing on stove 1 inwall. At present, for this dross thing, conventionally adopt in blowing out gap,Remove by mechanical system, for example, use chisel to cut, use spatula to root out etc. There are several drawbacks in mechanical removal mode:Due to dross thing or dross thing layer hardness very high, mechanical removal mode is difficult to remove clean; 2. mechanical removal mode is held very muchEasily refining furnace 1 inwall is caused damage, causing must follow-up repairing furnace wall; 3. mechanical removal mode, wastes time and energy, and makesThe off time between adjacent two heats is longer, thereby make the removing impurities oxid-reclamatiom cycle longer, had a strong impact on productionRhythm and production efficiency. For this reason, in one embodiment of the invention, when the cavity in refining furnace 1 is in atmospheric pressure shapeWhen state, by oxygen rifle 4 in the mode of top-blown gas to the interior winding-up fuel gas of refining furnace 1 and oxygen-containing gas, by combustible gasBody and oxygen-containing gas ignition combustion, the combustion reaction liberated heat that utilizes fuel gas and oxygen-containing gas to splash in refiningThe dross thing of the cooling rear formation of copper smelting slag liquation on stove 1 inwall melts to remove to be processed, and utilizes fuel gas and containsThe combustion reaction liberated heat of carrier of oxygen carries out baker processing to refining furnace 1; Oxygen rifle 4 is to comprise multiple inside and outside suitsThe multilayer internal and external casing structure of hollow pipe, oxygen rifle 4 comprises hollow by suit inside and outside the cavity in hollow pipe or adjacent twoThat cavity between the tube wall of pipe forms and for delivery of the fuel gas passage of fuel gas, fuel gas passage and flammableThe compressed air source unit of gas is communicated with; Oxygen rifle 4 also comprises by the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent twoThat cavity between tube wall forms and for delivery of the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage and oxygen-containing gasCompressed air source unit be communicated with; Oxygen rifle 4 also comprises and being formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent twoAnd for oxygen rifle 4 being carried out to the cool cycles aquaporin of cooling protection, cool cycles aquaporin and apparatus for supplying cool water connectLogical; Oxygen rifle 4 is arranged on the roof of refining furnace 1 and can slides up and down along the roof of refining furnace 1.
The present invention is when the cavity in refining furnace 1 is during in atmospheric pressure state, by oxygen rifle 4 in the mode of top-blown gas to essenceThe interior winding-up fuel gas of furnace 1 and oxygen-containing gas, by fuel gas and oxygen-containing gas ignition combustion, utilize fuel gas andThe cooling rear formation of copper smelting slag liquation on refining furnace 1 inwall to splash of the combustion reaction liberated heat of oxygen-containing gasDross thing melts to remove to be processed, and the temperature improving in refining furnace 1 upper space becomes dross thing melted by heat againBecome liquid, flow downward along the inwall of refining furnace 1, finally flow out refining furnace 1; Because oxygen rifle 4 is arranged on refining furnaceOn 1 roof and can slide up and down along the roof of refining furnace 1, make to remove after the dross thing at a certain position oxygen rifle4 can ascending motion or descending motion other position in refining furnace 1 melted to remove process, finally realize wholeOn individual refining furnace 1 inwall, the fusing of dross thing is removed, thereby has weakened a series of that above-mentioned mechanical removal mode bringsNegative influence.
In order further to understand the present invention, the money below in conjunction with embodiment to a kind of high impurity copper metallurgical slag provided by the inventionSource recovery method is elaborated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Taking the hot melt state smelting slag of flash smelting furnace discharge as handling object, temperature within the scope of 1280 DEG C, this copper smelting slagLiquation comprises the component of following percentage by weight: 1.2% copper, 0.72% lead, 5.88% zinc, 1.2% arsenic, 0.39%Antimony, 0.51% bismuth, 0.02% tin. Comprise the following steps:
1) the copper smelting slag liquation of melting is joined and contain in slag container 5; Then feed tube 2 and drain pipe 3 are immersedTo the following certain depth of upper liquid level of containing slag container 5 interior copper smelting slag liquations, then open vavuum pump by refining furnace 1The cavity state that is evacuated, now contains copper smelting slag liquation in slag container 5 along the cavity in feed tube 2 and drain pipe 3Passage rises and flows in the cavity of refining furnace 1;
2) to the driving gas with pressure of jetting in the copper smelting slag liquation in feed tube 2, contain slag container 5, feed tube 2,Between refining furnace 1 and drain pipe 3, form circulating of copper smelting slag liquation; Meanwhile, in refining furnace 1, to essenceCopper smelting slag liquation in furnace 1 blows oxygen-containing gas; Controlling vacuum residual voltage is 100Pa～300Pa; Control blowing of oxygenThe amount of sending is 7m3/ t slag, the copper smelting slag liquation after oxidation comprises bloodstone, cupric oxide ore and quartz mine;
3) step 2) carry out after a period of time, component and the content of the copper smelting slag liquation after sample examination removing impurities and oxidation,If lead content is less than 0.01%, and arsenic content is less than 0.05%, and result of laboratory test reaches target design requirement, removing impurities oxidation placeReason finishes, and be 25min writing time; Removing impurities oxidation processes finishes to obtain copper smelting slag liquation after removing impurities and oxidation, solidifyingThe oxide mixture of the impurity element of poly-state and the flue gas of being discharged by vavuum pump; Copper after gained removing impurities and oxidation is smeltedSlag liquation comprises the component of following percentage by weight: 0.0049% lead, 0.0022% zinc, 0.022% arsenic, 0.063%Antimony, 0.0062% bismuth, 0.0017% tin; Corresponding removal efficiency is respectively: lead: 99.32%, zinc: 99.96%,Arsenic: 98.17%, antimony: 83.85%, bismuth: 98.78%, tin: 91.5%;
4) then, above-mentioned Sheng slag container 5 is transported to slag slow cooling field, the copper smelting by removing impurities and after being oxidized with cinder ladle carSlag liquation first naturally cooling 24 hours, then the spraying cooling 36 hours of adding water. After above-mentioned slow cooling processing finishes, will contain slag and holdSlag in device 5 is poured out, with sending into ore grinding-ore-sorting system by belt after crusher in crushing. Slag is through grinding ore grindingAnd become the ore pulp of fineness within the scope of 85 order～325 orders, enter copper floatation system.
To first carry out active flotation through the copper smelting slag of slow cooling processing: the sulphur that adds 400g/t slag in activation tank diameterChange sodium, ore pulp is sized mixing, then enter in medicament tank diameter, add ethyl xanthogenate and the 100g/t of 300g/t slagThe terpenic oil of slag mixes with ore pulp, finally enters flotation device and carries out flotation, obtains after filtration grade and be 25% copper essenceOre deposit and active flotation mine tailing.
The ore pulp of active flotation mine tailing is introduced into iron floatation system: ore pulp is introduced into medicament tank diameter, in medicament tank diameterAdd the oxidized paraffin wax soap of 600g/t slag and the terpenic oil of 200g/t slag to mix with ore pulp, then enter flotation device and carry outFlotation, obtains grade and is 65% most of bloodstone iron ore concentrate and flotation tailing. The ore pulp of flotation tailing enters high intensity magnetic separationMachine carries out magnetic separation, obtains grade and be 65% remaining bloodstone iron ore concentrate and magnetic tailing.
The iron ore concentrate that flotation and magnetic separation obtain filters after merging, and obtains final iron ore concentrate; The mine tailing warp that magnetic separation obtainsFilter, obtain SiO2The siliceous product of content 85%.
Embodiment 2
Taking the hot melt state smelting slag of flash smelting furnace discharge as handling object, temperature within the scope of 1250 DEG C, this copper smelting slagLiquation comprises the component of following percentage by weight: 1.4% copper, 0.52% lead, 4.50% zinc, 1.0% arsenic, 0.23%Antimony, 0.25% bismuth, 0.02% tin. Comprise the following steps:
1) the copper smelting slag liquation of melting is joined and contain in slag container 5; Then feed tube 2 and drain pipe 3 are immersedTo the following certain depth of upper liquid level of containing slag container 5 interior copper smelting slag liquations, then open vavuum pump by refining furnace 1The cavity state that is evacuated, now contains copper smelting slag liquation in slag container 5 along the cavity in feed tube 2 and drain pipe 3Passage rises and flows in the cavity of refining furnace 1;
2) to the driving gas with pressure of jetting in the copper smelting slag liquation in feed tube 2, contain slag container 5, feed tube 2,Between refining furnace 1 and drain pipe 3, form circulating of copper smelting slag liquation; Meanwhile, in refining furnace 1, to essenceCopper smelting slag liquation in furnace 1 blows oxygen-containing gas; Controlling vacuum residual voltage is 300Pa～500Pa; Control blowing of oxygenThe amount of sending is 7m3/ t slag, the copper smelting slag liquation after oxidation comprises bloodstone, cupric oxide ore and quartz mine;
3) step 2) carry out after a period of time, component and the content of the copper smelting slag liquation after sample examination removing impurities and oxidation,If lead content is less than 0.01%, and arsenic content is less than 0.05%, and result of laboratory test reaches target design requirement, removing impurities oxidation placeReason finishes, and be 30min writing time; Removing impurities oxidation processes finishes to obtain copper smelting slag liquation after removing impurities and oxidation, solidifyingThe oxide mixture of the impurity element of poly-state and the flue gas of being discharged by vavuum pump; Copper after gained removing impurities and oxidation is smeltedSlag liquation comprises the component of following percentage by weight: 0.0033% lead, 0.0019% zinc, 0.025% arsenic, 0.023%Antimony, 0.0042% bismuth, 0.0019% tin; Corresponding removal efficiency is respectively: lead: 99.37%, zinc: 99.96%,Arsenic: 97.5%, antimony: 90%, bismuth: 98.32%, tin: 90.5%;
4) then, above-mentioned Sheng slag container 5 is transported to slag slow cooling field, the copper smelting by removing impurities and after being oxidized with cinder ladle carSlag liquation first naturally cooling 24 hours, then the spraying cooling 36 hours of adding water. After above-mentioned slow cooling processing finishes, will contain slag and holdSlag in device is poured out, with sending into ore grinding-ore-sorting system by belt after crusher in crushing. Slag through grinding ore grinding andBecome the ore pulp of fineness within the scope of 85 order～325 orders, enter copper floatation system.
To first carry out active flotation through the mixing slag charge of slow cooling processing: the sulphur that adds 400g/t slag in activation tank diameterChange sodium, ore pulp is sized mixing, then enter in medicament tank diameter, add ethyl xanthogenate and the 100g/t slag of 300g/t slagTerpenic oil mix with ore pulp, finally enter flotation device and carry out flotation, obtain after filtration grade and be 25% copper concentrateWith active flotation mine tailing.
The ore pulp of active flotation mine tailing is introduced into iron high intensity magnetic separation system, obtains iron rough concentrate and high intensity magnetic separation tail after high intensity magnetic separationOre deposit, then iron rough concentrate, through sizing mixing, adds the lauryl amine of 300g/t slag and the terpenic oil of 150g/t slag to carry out reverse flotation,After filtration, obtain grade and be 65% bloodstone iron ore concentrate and reverse flotation mine tailing.
Reverse flotation mine tailing and high intensity magnetic separation mine tailing filter after merging, and obtain SiO2Content is 85% siliceous product.
The present invention is directed to the technical problem of wanting solution, provide multiple laddering technical schemes, multiple laddering skillsArt scheme combines stack mutually, cooperatively interacts, and mutually promotes, and forms an overall plan, and the technique effect of obtaining is far goodIn the technique effect of above-mentioned any one technical scheme, synergistic effect is remarkable.
The present invention not method and apparatus of detailed description is prior art, repeats no more.
In this description, each embodiment adopts the mode of going forward one by one to describe, and what each embodiment stressed is real with otherExecute routine difference, between each embodiment same or similar part mutually referring to.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof. It should be pointed out that forThose skilled in the art, under the premise without departing from the principles of the invention, can also carry out the present inventionSome improvement and modification, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention. RightApparent for those skilled in the art in the multiple amendment of these embodiment, defined herein oneAs principle can be in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, thisBrightly will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of noveltyConsistent wide region.
Claims (6)
1. a resource recycle method for high impurity copper metallurgical slag, is characterized in that, comprises the following steps:
1) the copper smelting slag liquation of melting is joined to the Sheng slag container for splendid attire copper smelting slag liquation; Then will establishPut upper liquid level that feed tube on refining furnace diapire and drain pipe be immersed in copper smelting slag liquation in described Sheng slag container withLower certain depth, then opens the vavuum pump that is communicated with described refining furnace by the shape that is evacuated of the cavity in described refining furnaceState, now in refining furnace under the effect of the atm difference between vacuum residual voltage and external atmosphere pressure in described Sheng slag containerCopper smelting slag liquation rises and flows in the cavity of described refining furnace along the cavity passage in described feed tube and described drain pipe;
The profile of described refining furnace is vertical column, inner hollow form cavity, described refining furnace comprise steel shell andBuild the refractory lining at described steel shell inner surface by laying bricks or stones, the top of described refining furnace be provided with for described vacuumThe gas outlet that pump connects;
Described feed tube and described drain pipe include steel inner casing, are arranged on the fire proofed wood of the inner surface of described steel inner casingExpect liner and be arranged on the refractory material outer lining of the outer surface of described steel inner casing;
Described feed tube and described drain pipe be fixedly installed on the diapire of described refining furnace and with the diapire of described refining furnaceBe tightly connected, the cavity passage in the cavity in described refining furnace and described feed tube is interconnected, in described refining furnaceCavity passage in cavity and described drain pipe is interconnected, the device that all and described refining furnace is connected with described refiningEncapsulation process is all carried out to prevent from destroying the vacuum state in described refining furnace in the position that stove connects;
2) to the driving gas with pressure of jetting in the copper smelting slag liquation in described feed tube, then in atm difference and driveThe copper smelting slag liquation in described Sheng slag container under the drive of body of taking offence is constantly risen and is flowed into described essence by described feed tubeIn furnace, then the copper smelting slag liquation in described refining furnace is constantly flowed out by described refining furnace by described drain pipe againBe back in described Sheng slag container, between described Sheng slag container, feed tube, refining furnace and drain pipe, form copper and smeltCirculating of slag liquation;
Meanwhile, in described refining furnace, the copper smelting slag liquation in described refining furnace blows oxygen-containing gas;
Utilize oxygen element in oxygen-containing gas by impurity element oxygen included in the copper smelting slag liquation in described refining furnaceChange into the oxide of corresponding impurity element, the oxide of the impurity element that oxidation forms becomes gaseous oxygen under vacuum environmentCompound volatilization removes, and realizes the process that removes impurity element in copper smelting slag;
Then the gas that is mixed with the oxide of the impurity element of gaseous state enters the condenser being communicated with described refining furnace by coldSolidifying, obtain the oxide mixture of the impurity element of condensed condensed state, realize and reclaim impurity element in copper smelting slagProcess;
Described impurity element comprise in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;
Utilize the oxidation of the oxygen element in oxygen-containing gas by the oxidation of copper smelting slag liquation, make the copper smelting slag after oxidationLiquation comprises bloodstone, cupric oxide ore and quartz mine, realizes the process of copper smelting slag oxidation;
3) described step 2) carry out after a period of time, sample examination removing impurities and oxidation after copper smelting slag liquation component andFirst content, if result of laboratory test reaches target design requirement, abolish the vacuum state in described refining furnace, then will establishFeed tube and the drain pipe put on described refining furnace diapire depart from the copper smelting slag liquation in described Sheng slag container, removing impurities oxygenChanging processing finishes; If the designing requirement of result of laboratory test miss the mark, continues removing impurities oxidation processes, until result of laboratory test reachesTarget design requirement;
Removing impurities oxidation processes finishes to obtain the oxide of the impurity element of copper smelting slag liquation after removing impurities and oxidation, condensed stateMixture and the flue gas of being discharged by described vavuum pump;
4) by step 3) first copper smelting slag liquation after the removing impurities that obtains and oxidation pass through slow cooling processing, then will pass throughThe copper smelting slag of slow cooling processing first carries out active flotation, obtains copper concentrate and active flotation mine tailing, then to described active flotationMine tailing carries out flotation and magnetic separation, obtains bloodstone, finally the mine tailing reclaiming after bloodstone is filtered, and obtains siliceous productProduct, realize the process that reclaims iron, copper and element silicon in copper smelting slag.
2. resource recycle method according to claim 1, is characterized in that, described step 2) in, contain describedThe mode that carrier of oxygen blows with submergence blows to the upper liquid level of the copper smelting slag liquation in described refining furnace, described in ejectionThe gas outlet of oxygen-containing gas is positioned at below the upper liquid level of copper smelting slag liquation of described refining furnace.
3. resource recycle method according to claim 1 and 2, is characterized in that, described step 2) in, pass throughOxygen rifle blows described oxygen-containing gas to the copper smelting slag liquation in described refining furnace in the mode of top-blown gas, described oxygenThe gas outlet of rifle be positioned at the upper liquid level of copper smelting slag liquation of described refining furnace above and with the upper liquid of copper smelting slag liquationFace in a distance;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and contain for delivery of describedThe oxygen-containing gas passage of carrier of oxygen, described oxygen-containing gas passage is communicated with the compressed air source unit of described oxygen-containing gas;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle also comprises for improving described oxygen-containing gas spouting velocity and controlling described oxygen-containing gas injection directionShower nozzle, described shower nozzle is arranged on the bottom of described oxygen rifle, and the gas outlet of described oxygen rifle is arranged on described shower nozzle;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
4. resource recycle method according to claim 1, is characterized in that, described step 2) in, when described essenceCavity in furnace in the time of vacuum state, by oxygen rifle in the mode of top-blown gas to the combustible gas of jetting in described refining furnaceBody and oxygen-containing gas, by described fuel gas and described oxygen-containing gas ignition combustion, utilize described fuel gas and described containingThe combustion reaction liberated heat of carrier of oxygen carries out supplementary heating processing to the copper smelting slag liquation in described refining furnace, utilizesThe combustion reaction liberated heat of described fuel gas and described oxygen-containing gas is the copper on described refining furnace inwall to splashThe dross thing of the cooling rear formation of metallurgical slag liquation is removed processing;
The gas outlet of described oxygen rifle is positioned at above and and the copper smelting slag of the upper liquid level of copper smelting slag liquation of described refining furnaceThe upper liquid level of liquation in a distance;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and for delivery of described canThe fuel gas passage of combustion gas body, described fuel gas passage is communicated with the compressed air source unit of described fuel gas;
Described oxygen rifle also comprises by the sky between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent twoThat chamber forms and for delivery of the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage and described oxygen-containing gasCompressed air source unit be communicated with;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
5. resource recycle method according to claim 1, is characterized in that, when the cavity place in described refining furnaceIn the time of atmospheric pressure state, by oxygen rifle in the mode of top-blown gas to the fuel gas and oxygenous of jetting in described refining furnaceBody, by described fuel gas and described oxygen-containing gas ignition combustion, utilizes the combustion of described fuel gas and described oxygen-containing gasThe dross thing that burns the cooling rear formation of copper smelting slag liquation on described refining furnace inwall to splash of reaction liberated heat entersRow fusing is removed and is processed, and utilizes the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas to described refiningStove carries out baker processing;
Described oxygen rifle is the multilayer internal and external casing structure that comprises the hollow pipe of multiple inside and outside suits, and described oxygen rifle comprises by hollowThat cavity inside and outside cavity in pipe or adjacent two between the tube wall of the hollow pipe of suit forms and for delivery of described canThe fuel gas passage of combustion gas body, described fuel gas passage is communicated with the compressed air source unit of described fuel gas;
Described oxygen rifle also comprises by the sky between the tube wall of the hollow pipe of suit inside and outside the cavity in hollow pipe or adjacent twoThat chamber forms and for delivery of the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage and described oxygen-containing gasCompressed air source unit be communicated with;
Described oxygen rifle also comprise formed by the cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for rightDescribed oxygen rifle carries out the cool cycles aquaporin of cooling protection, and described cool cycles aquaporin and apparatus for supplying cool water connectLogical;
Described oxygen rifle is arranged on the roof of described refining furnace and can slides up and down along the roof of described refining furnace.
6. resource recycle method according to claim 1, is characterized in that, described step 1) in, described copper smeltingThe copper grade of refining slag liquation is less than or equal to 3%.
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