CN117025970A - Method for synchronously recycling metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag - Google Patents
Method for synchronously recycling metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag Download PDFInfo
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- CN117025970A CN117025970A CN202310801607.9A CN202310801607A CN117025970A CN 117025970 A CN117025970 A CN 117025970A CN 202310801607 A CN202310801607 A CN 202310801607A CN 117025970 A CN117025970 A CN 117025970A
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- 238000002386 leaching Methods 0.000 title claims abstract description 307
- 239000012141 concentrate Substances 0.000 title claims abstract description 259
- 239000010949 copper Substances 0.000 title claims abstract description 236
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 212
- 239000002893 slag Substances 0.000 title claims abstract description 189
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 92
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 92
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000004064 recycling Methods 0.000 title claims description 6
- 238000005188 flotation Methods 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 59
- 238000011282 treatment Methods 0.000 claims description 40
- 230000002000 scavenging effect Effects 0.000 claims description 16
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- 230000008569 process Effects 0.000 description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- 230000002195 synergetic effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
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- 238000006243 chemical reaction Methods 0.000 description 9
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- 229910001779 copper mineral Inorganic materials 0.000 description 8
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- -1 chlorine ions Chemical class 0.000 description 5
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 238000003912 environmental pollution Methods 0.000 description 4
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- 239000008396 flotation agent Substances 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
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- 229910000859 α-Fe Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052927 chalcanthite Inorganic materials 0.000 description 3
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 2
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052971 enargite Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 239000002918 waste heat 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application belongs to the technical field of nonferrous metal smelting, and discloses a method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag, which comprises the following steps: carrying out acid flotation on the copper oxide concentrate leaching slag to obtain slag-separated copper concentrate with Cu grade of 6-10%; mixing the obtained slag copper concentrate with copper sulfide concentrate calcine leaching slag to obtain mixed ore; stirring and mixing the obtained mixed ore and a leaching agent to obtain slurry; leaching the obtained slurry at 80-90 ℃ and carrying out solid-liquid separation to obtain leaching residues and leaching liquid; washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching solution to obtain a loaded organic phase and raffinate, and carrying out back extraction and electrodeposition on the obtained loaded organic phase to obtain the metallic copper. The application effectively and synergistically leaches the slag of the slag copper concentrate and the calcine leaching slag of the copper sulfide concentrate, the leaching rate is more than 82 percent, and the comprehensive recovery of copper resources in smelting waste slag can be realized.
Description
Technical Field
The application relates to the technical field of hydrometallurgy, in particular to a method for synchronously recycling metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag.
Background
The method is an important research topic for improving the resource integration of nonferrous metal production enterprises from the dotted line surface by continuously optimizing, improving, innovating and sublimating the traditional metallurgical process, optimizing the process flow, developing a new metallurgical process and adopting a refined treatment method to realize the value conversion of industrial pollution in the enterprise production process.
According to the report of China mineral resource report issued by the natural resource department 2022 of the people's republic of China, 3494.79 ten thousand tons of copper ore reserves (metal quantity) are reserved nationally by the end of 2021, 185.5 ten thousand tons of copper concentrate yield and 1048.7 ten thousand tons of refined copper yield are reserved nationally. However, most copper ores in China are mixed ores formed by complex copper sulfide and oxidized ores associated with multiple elements. At present, copper ores in Africa areas, particularly Congo (gold), are basically mixed ores of sulphide ores and oxide ores, most of the mixed ore treatment processes are that copper oxide concentrate and copper sulphide concentrate are produced by firstly carrying out sulfur-then-oxygen flotation, the copper oxide concentrate enters a hydrometallurgical system, the copper sulphide concentrate is roasted to produce calcine and then enters the hydrometallurgical system, and the copper oxide minerals and the copper sulphide minerals are continuously mixed in the flotation process due to finer granularity or non-uniformity of the ore apology in the firstly-sulfur-then-oxygen flotation process, so that the copper oxide minerals and the copper sulphide minerals contain sulfide minerals which cannot be leached by a conventional wet method; meanwhile, the calcine produced by roasting the copper sulfide concentrate contains insufficiently oxidized copper minerals in a sulfurized state. Thus causing the two concentrate wet leaching residues to contain a large amount of unrecovered copper metal.
The copper grade in the low-grade copper oxide concentrate leaching slag is generally 1% -3%, and the leaching slag is obtained after leaching the copper oxide concentrate product produced by adopting a process of firstly floating copper sulfide and then floating copper oxide for complex mixed ores. The copper grade in the copper sulfide concentrate calcine leaching slag is generally 4% -8%, and the copper grade is leaching slag obtained by two-stage leaching of the calcine obtained by roasting high-grade copper sulfide concentrate. At present, single treatment of the low-grade leaching slag products is difficult, most leaching slag is piled up in a slag yard, and a great deal of copper resources are wasted while environmental pollution is caused. However, copper resources are non-renewable resources, and as humans continue to consume, reserves gradually decrease, and problems of the existing processes in treating "lean, fine, and miscellaneous" ores are increasingly prominent. Therefore, how to recover copper metal from complex low-grade leaching slag has become a difficult point and an important development direction in the industry.
Currently, when the hydrometallurgy is faced with difficult-to-process complex low-grade copper oxide leaching slag and copper sulfide concentrate calcine leaching slag, the processing method mainly focuses on several directions such as pressure leaching, chloride leaching, ammonia leaching, bioleaching and the like. But the pressure leaching has large investment, high energy consumption and high requirements on equipment performance; the chlorine salt leaching process can only treat copper ores with Cu grade of more than 25%, the solid-liquid separation amount in the whole process is large, the chlorine ions brought into the system in the treatment process can accelerate equipment corrosion while influencing the cathode copper quality, and the requirement on the equipment corrosion resistance is high; the ammonia leaching method has great harm to human body and serious environmental pollution, and the required environmental protection investment is large; biological leaching, namely biological metallurgy, is a product of the cross interaction of microbiology and hydrometallurgy, but microorganisms can be leached effectively only by domestication or mutation breeding, and the microbial community is difficult to culture, the period is long, the leaching rate is low, and the microbial community is limited by multiple conditions such as regional conditions, natural environment, ore properties and the like, so that the microbial community is difficult to apply to large scale in China. In view of the multiple condition limitations of extracting copper by the treatment process, the existing low-grade copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag which have complex structures and coexistent multiple elements are not provided with a better treatment process, so that the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag are piled up or abandoned in a large amount due to the difficulty in recovering copper metal, and great environmental protection pressure is brought while the waste of copper resources is caused.
Disclosure of Invention
The application provides a method for synchronously recovering metal copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag, which aims to solve the technical problems of copper resource waste and environmental pollution caused by the fact that the low-grade complex copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag are difficult to recover metal copper in the prior art.
The application provides a method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag, wherein the Cu grade of the copper oxide concentrate leaching slag is 1-3%, and the Cu grade of the copper sulfide concentrate calcine leaching slag is 4-8%, and the method comprises the following steps:
(1) Carrying out acid flotation on the copper oxide concentrate leaching slag to obtain slag-separated copper concentrate with Cu grade of 6-10%;
(2) The obtained slag copper concentrate and copper sulfide concentrate calcine leaching slag are subjected to slag separation according to the mass ratio of 1: mixing the materials according to the proportion of (1-1.2) to obtain mixed ore;
(3) Stirring and mixing the obtained mixed ore and a leaching agent to obtain slurry, wherein the leaching agent is a sulfuric acid solution system leaching agent; the mass concentration of the slurry is 15-17%;
(4) Leaching the obtained slurry at 80-90 ℃ and carrying out solid-liquid separation to obtain leaching residues and leaching liquid;
(5) Washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching solution to obtain a loaded organic phase and a raffinate, wherein the obtained washing liquid is used in the extraction step, and the obtained washing slag is subjected to tail removal treatment; the raffinate obtained by extraction is used for preparing the sulfuric acid solution system leaching agent;
(6) And carrying out back extraction and electrodeposition on the obtained loaded organic phase to obtain the metallic copper.
Further, the step (1) of performing acid flotation on the copper oxide concentrate leaching slag comprises the following steps:
(a) Mixing the copper oxide concentrate leaching slag with water to obtain ore pulp, wherein the mass percentage concentration of the ore pulp is 15-25%;
(b) Adding a collector and a foaming agent into the obtained ore pulp for roughing to obtain rough concentrate and roughing tailings;
(c) Carrying out first concentration and second concentration on the obtained rough concentrate to obtain slag-separated copper concentrate; scavenging the obtained roughing tailings to obtain copper scavenging middlings and tailings, wherein the copper scavenging middlings enter a first concentration step, and the tailings are subjected to tailing discharge.
Further, the collector in the step (b) is dithiocarbonic acid-O-butyl sodium salt, and the addition amount is 100-300 g/ton copper oxide concentrate leaching slag.
Further, in the step (b), the foaming agent is pine oil, and the addition amount is 30-50 g/ton copper oxide concentrate leaching slag.
Further, the first beneficiation in step (c) produces copper middlings and copper beneficiation concentrate, the copper middlings returning to the roughing step; the copper concentrate enters a second beneficiation.
Further, the second concentration in the step (c) produces copper middling second and slag copper concentrate, the copper middling second returns to the first concentration step, and the slag copper concentrate is slag copper concentrate with the Cu grade of 6-10%.
Further, in the step (3), the particles with the particle size smaller than 0.074mm account for 70-80% of the total particle weight in the slurry.
Further, the leaching time of the slurry obtained by leaching in the step (4) at 80-90 ℃ is more than 6 hours.
Further, the step (4) further comprises concentrating the leached slurry before solid-liquid separation.
Further, the step (5) of washing the obtained leaching residue comprises stirring and washing the obtained leaching residue with clear water with the pH value of 6.5-7.5 under natural conditions.
The application has the following beneficial effects:
according to the application, acid flotation is carried out on copper oxide concentrate leaching slag, preliminary enrichment is carried out on copper sulfide minerals which are easy to float in the copper oxide concentrate leaching slag, ore blending, slurry mixing, heating leaching and other processes are adopted on the slag copper concentrate and copper sulfide concentrate calcine leaching slag, effective synergistic leaching is carried out on copper sulfide and copper ferrite which are difficult to be singly treated in the slag copper concentrate and copper sulfide concentrate calcine leaching slag, and finally the synergistic leaching rate of the obtained slag copper concentrate and copper sulfide concentrate calcine leaching slag is more than 82%.
The essence of the synergistic treatment process provided by the application is that the copper oxide concentrate leaching slag is enriched firstly, and then the solid raw materials of the slag copper concentrate and copper sulfide concentrate calcine leaching slag obtained by enrichment are leached directly. The leaching system is composed of slag selected copper sulfide concentrate, copper sulfide concentrate calcine leaching slag, sulfuric acid and water phase, and valuable metals such as Cu and the like which are difficult to leach in the materials are continuously converted into soluble sulfate at the temperature of 80-90 ℃ so that the soluble sulfate enters the solution in an ionic form for recycling. The synergistic treatment process has strong practicability on low-grade copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag with complex structures and changeable properties, effectively realizes the synergistic treatment of the low-grade copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag, has low leaching cost and simple and mature subsequent treatment process, and greatly reduces the copper content in the final leaching slag by carrying out the treatment on the complex low-grade copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag, thereby avoiding the massive piling and waste of leached tailings generated in the exploitation and processing process of copper products.
In addition to the objects, features and advantages described above, the present application has other objects, features and advantages. The present application will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is a schematic diagram of a process flow of a low-grade copper-cobalt mixed ore according to a preferred embodiment of the application;
FIG. 2 is a schematic illustration of a process flow for preparing a slag-beneficiated copper concentrate from a copper oxide concentrate leaching slag in accordance with a preferred embodiment of the present application;
FIG. 3 is a schematic diagram of the co-processing process of slag-separated copper concentrate and copper sulfide concentrate calcine leaching slag in accordance with a preferred embodiment of the present application;
fig. 4 is a schematic view of a co-processing apparatus for slag-separated copper concentrate and copper sulfide concentrate calcine leaching slag in accordance with a preferred embodiment of the present application.
Legend description:
1-a size mixing tank; 2-a feed valve; 3-a feed pump; 4-a stirrer; 5-a leaching tank; 6-a digital display thermometer; 7-a discharge valve; 8-a discharge pump; a 9-sulfuric acid pipe; 10-sulfuric acid flowmeter; 11-sulfuric acid valve; 12-a clear water pipeline; 13-a flow meter; 14-controlling a valve; 15-a steam pipe; 16-steam valve.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present application clearer, the present application will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the application only and are not intended to limit the application.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
The embodiment of the application provides a method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag, wherein the Cu grade of the copper oxide concentrate leaching slag is 1-3%, and the Cu grade of the copper sulfide concentrate calcine leaching slag is 4-8%, and the method comprises the following steps:
(1) Carrying out acid flotation on the copper oxide concentrate leaching slag to obtain slag-separated copper concentrate with Cu grade of 6-10%;
(2) The obtained slag copper concentrate and copper sulfide concentrate calcine leaching slag are subjected to slag separation according to the mass ratio of 1: mixing the materials according to the proportion of (1-1.2) to obtain mixed ore;
(3) Stirring and mixing the obtained mixed ore and a leaching agent to obtain slurry, wherein the leaching agent is a sulfuric acid solution system leaching agent; the mass concentration of the slurry is 15-17%;
(4) Leaching the obtained slurry at 80-90 ℃ and carrying out solid-liquid separation to obtain leaching residues and leaching liquid;
(5) Washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching solution to obtain a loaded organic phase and a raffinate, wherein the obtained washing liquid is used in the extraction step, and the obtained washing slag is subjected to tail removal treatment; the raffinate obtained by extraction is used for preparing the sulfuric acid solution system leaching agent;
(6) And carrying out back extraction and electrodeposition on the obtained loaded organic phase to obtain the metallic copper.
In the embodiment of the application, the copper sulfide concentrate calcine leaching slag is copper sulfide concentrate with copper grade of 60-70% obtained by flotation of copper-cobalt mixed ore with grade of 2-4% through a process of firstly flotation copper sulfide and then flotation copper oxide, the copper sulfide concentrate is subjected to oxidative roasting and partial acidification roasting to obtain calcine with grade of 50-60%, the calcine is subjected to sulfuric acid leaching process to obtain final copper sulfide concentrate calcine leaching slag, and the copper grade in the copper sulfide concentrate calcine leaching slag is 4-8%.
In the embodiment of the application, the copper oxide concentrate leaching slag is copper oxide concentrate with copper grade of 15-25% obtained by flotation of copper sulfide and copper cobalt mixed ore with grade of 2-4% through a flotation process and a sulfuric acid leaching process, and the final copper oxide concentrate leaching slag is obtained by flotation of copper concentrate, wherein the grade of copper in the copper oxide concentrate leaching slag is about 1-3%.
In the examples of the present application, the term "copper concentrate from slag separation" as used herein refers to an intermediate product obtained by acid flotation of "copper concentrate leaching residue of copper oxide concentrate" having a Cu grade of 1 to 3%, wherein the copper grade is about 6 to 10%.
According to an exemplary embodiment of the present application, the production method of the copper sulfide concentrate calcine leaching slag and the copper oxide concentrate leaching slag is shown in fig. 1. Fig. 1 shows a simple production process of copper sulphide concentrate calcine leaching and copper oxide concentrate leaching.
In an embodiment of the present application, the acid flotation of the copper oxide concentrate leaching residue in the step (1) includes the following steps:
(a) Mixing the copper oxide concentrate leaching slag with water to obtain ore pulp, wherein the mass percentage concentration of the ore pulp is 15-25%;
(b) Adding a collector and a foaming agent into the obtained ore pulp for roughing to obtain rough concentrate and roughing tailings;
(c) Carrying out first concentration and second concentration on the obtained rough concentrate to obtain slag-separated copper concentrate; scavenging the obtained roughing tailings to obtain copper scavenging middlings and tailings, wherein the copper scavenging middlings enter a first concentration step, and the tailings are subjected to tailing discharge.
According to an exemplary embodiment of the present application, the treatment method of the copper oxide concentrate leaching residue is shown in fig. 2. Fig. 2 shows a schematic diagram of a process flow for preparing slag-separated copper concentrate from copper oxide concentrate leaching slag. The treatment method comprises the steps of preparing ore pulp and floatation treatment. Wherein, the preparation of ore pulp refers to the preparation of ore pulp by a mixture of copper oxide concentrate leaching slag and water, wherein, particles with the particle size of less than 0.074mm in the ore pulp account for 70-80% of the total particle weight; the flotation treatment comprises rougher and cleaner in turn.
According to a preferred embodiment of the application, the pulp has a concentration of 15-25% and a pH of 3-5. The copper oxide concentrate is leached by acid to obtain copper oxide concentrate leaching residue, the concentrate leaching residue is in a solid-liquid coexisting state, and the copper oxide concentrate leaching residue is mixed with water and subjected to pulp mixing and floatation. The application preferably controls the mass percentage concentration of the ore pulp to be 15-25% and sends the ore pulp to the flotation tank for flotation, because the recovery rate of slag-to-copper concentrate needed in the subsequent treatment process is considered at the same time. When the ore pulp concentration in the range is subjected to flotation, the recovery rate of copper in the slag-separated copper concentrate can be ensured; when the concentration of the ore pulp is lower than 15% or higher than 25%, flotation is performed, which is not beneficial to improving the recovery rate of Cu in the slag copper concentrate. The pH value of the ore pulp system is 3-5, the natural pH value is presented after the leaching slag of the copper oxide concentrate is reduced by the aqueous solution, the flotation is carried out within the pH value range, and the recovery rate of copper in the leaching slag of the copper oxide concentrate is not influenced.
According to a preferred embodiment of the application, the flotation treatment comprises a roughing step and a beneficiation step, wherein the roughing step comprises adding a collector and a foaming agent into the ore pulp, stirring and separating to obtain rough concentrate and roughing tailings; the selection step comprises stirring and sorting the rough concentrate for 2 times, wherein the stirring and sorting time of the first time is 8-10 minutes, and the stirring and sorting time of the second time is 16-20 minutes.
According to the embodiment of the application, the main purpose of roughing is to recover copper minerals in the copper oxide concentrate leaching slag, and one roughing is sufficient to enable 50-80% of the copper minerals to float out. The specific operation is that ore pulp with certain concentration is sent into a flotation tank, and a collector and a foaming agent are added into an ore pulp system in the flotation tank while stirring; the collector is added to float copper sulfide in ore pulp, and the action principle of the collector is that the collector acts with the surface of copper minerals to form chemical adsorption, so that the hydrophobic water property of the copper minerals is increased, and the copper minerals are adhered to foam and float together with the foam; the foaming agent is added to increase the amount of foam and its viscosity during foaming, facilitating adhesion of the copper mineral to the surface of the foam. The stirring is to mix the flotation reagent such as the collector and the frother with the pulp more sufficiently, and the stirring time may be generally 31 minutes, and the time is controlled within this range so that the copper mineral and the flotation reagent are mixed sufficiently.
In the embodiment of the application, in the step (b), the collector in the roughing stage is dithiocarbonic acid-O-butyl sodium salt, and the addition amount is 100-300 g/ton copper oxide concentrate leaching slag. The foaming agent is pine oil, and the addition amount is 30-50 g/ton copper oxide concentrate leaching slag.
In the embodiment of the application, the tailings after roughing are fed into a next foam tank for scavenging, and the foam product obtained by scavenging and the foam product obtained by roughing are fed into the next foam tank for fine selection. Wherein, the flotation reagent in the scavenging stage can comprise a collector thiocarbonate-O-butyl sodium salt and a foaming agent pinitol oil; the addition amount of dithiocarbonic acid-O-butyl sodium salt in the copper scavenging step is 30 g/ton copper oxide concentrate leaching residue; the addition amount of the pinitol oil is 5-10 g/ton copper oxide concentrate leaching residue; the scavenging time may be 5-10 minutes.
In an embodiment of the application, the resulting coarse concentrate is subjected to a first concentration and a second concentration in step (c), said first concentration producing copper middling and copper concentrate, said copper middling returning to the roughing step; the copper concentrate enters a second beneficiation.
In an embodiment of the application, the second concentration in step (c) produces copper middlings and slag-separated copper concentrate, the copper middlings returning to the first concentration step, the slag-separated copper concentrate being a slag-separated copper concentrate having a Cu grade of 6-10%.
According to the embodiment of the application, the rough concentrate obtained in the rough concentration step and the scavenging concentrate obtained in the scavenging step are concentrated, and the concentration of the ore pulp entering the concentration step is reduced by about 10-15% relative to the concentration of the ore pulp in the rough concentration step. The selection step may be performed by adding a flotation reagent and stirring. Blank beneficiation, as referred to herein, "blank beneficiation" means beneficiation without any flotation agents added, but by agitation. Because the ore particles in the ore pulp are adsorbed with the flotation agents on the surface in the course of roughing treatment, the adsorbed flotation agents can float copper sulfide out of the ore pulp in the stirring process, so that the blank concentration can be directly carried out without adding the flotation agents.
The specific concentration process is shown in figure 2, the concentration of the application is continuous 2-level blank concentration, and each blank concentration respectively obtains copper concentration middlings and copper concentration tailings. The first-stage blank concentration step is used for obtaining copper concentrate I and copper concentrate tailing I, wherein the copper concentrate I enters the second-stage blank concentration, and the copper concentrate tailing I returns to the roughing step of the previous stage; and (3) obtaining copper concentrate and copper tailings II in the second-stage blank concentration step, wherein the copper tailings II return to the first-stage blank concentration. Concentrate is selected as the final slag copper concentrate.
In the embodiment of the application, as shown in fig. 3-4, in the step (2), slag copper concentrate and copper sulfide concentrate calcine leaching slag with similar grades accounting for 70-80% of particles with the particle size of 0.074mm are mixed according to the proportion of 1:1-1:1.2. And conveying the mixed ore obtained after mixing into a slurry mixing tank 1, adding the prepared leaching agent, and uniformly stirring to perform slurry mixing. Wherein the leaching agent is a sulfuric acid solution system, sulfuric acid solution is fed through a sulfuric acid pipe 9, the sulfuric acid consumption is controlled by a sulfuric acid flowmeter 10 and a sulfuric acid valve 11, and the concentration of sulfuric acid at the beginning of leaching is 2-3.5mol/L.
The well-regulated slurry is then conveyed to a leaching tank 5 for leaching through a feed valve 2 and a feed pump 3 (a discharge valve 7 is arranged at the bottom of the leaching tank 5, and the discharge valve 7 is connected with a discharge pump 8 and is matched with the discharge pump for discharging after leaching is finished). The solid-liquid ratio during leaching is 1:5, a steam valve 16 is opened, steam enters from a steam pipeline 15, the temperature in the leaching tank 5 rises, a digital display thermometer 6 can display the temperature in the leaching tank 5, the temperature in the leaching tank 5 is controlled to be 80-90 ℃, preferably 85 ℃ through the steam valve 16, and stirring leaching is performed through a stirrer 4. The specific heating mode can be to heat by using the waste heat boiler steam of the roasting furnace.
The co-treatment device in fig. 4 further comprises a clean water conduit 12, the clean water conduit 12 being in communication with the size mixing tank 1 via a control valve 14 and with the leaching tank 5 via a flowmeter 13, said leaching tank 5 being provided with one or more.
Under the above conditions, valuable metallic copper mainly existing in minerals such as silica, chalcanthite, copper ferrite, copper blue and copper maceraite in the mixed ore reacts with other substances in quartz, gypsum, magnetite, kaolinite, muscovite, chlorite and rutile, and enters the solution in an ionic form to be converted into soluble sulfate. The main reactions occurring in the co-leaching process are as follows:
cu in ore 2 O·Fe 2 O 3 And CuFe 2 O 4 The following reactions take place in an aqueous solution of sulfuric acid:
2Cu 2 O·Fe 2 O 3 +4H 2 SO 4 +O 2 ＝4CuSO 4 +2Fe 2 O 3 +4H 2 O (1)
CuO·Fe 2 O 3 +H 2 SO 4 ＝CuSO 4 +Fe 2 O 3 +H 2 O (2)
CuFe 2 O 4 +H 2 SO 4 +2H 2 O＝CuSO 4 +2Fe(OH) 3 (3)
CuFe 2 O 4 +H 2 SO 4 ＝CuSO 4 +Fe 2 O 3 +H 2 O (4)
sulfide such as CuS in ore is coated with Cu 2 O·Fe 2 O 3 And CuFe 2 O 4 Fe produced by reaction with sulfuric acid 3+ Oxidizing to regenerate S o 、Cu 2+ ，Fe 3+ Itself is reduced to Fe 2+ . The overall reaction that occurs during leaching is as follows:
2CuS+2H 2 SO 4 +O 2 ＝2CuSO 4 +2S+2H 2 O (5)
the reaction process of CuS in the specific copper oxide concentrate leaching slag in the solution is as follows:
CuS has an ionization balance in solution:
CuS＝Cu 2+ +S 2－ (6)
ionized S 2－ The ions are changed into hydrogen sulfuric acid by sulfuric acid in the system:
S 2－ +2H + ＝H 2 S (7)
since hydrogen sulfuric acid is a weak acid, S in an acidic solution 2－ Almost all exists in the form of hydrogen sulfate. Meanwhile, the hydrogen sulfuric acid is dissolved by Fe 3+ Oxidizing elemental sulfur:
H 2 S+2Fe 3+ →2H + +S↓+2Fe 2+ (8)
the generated elemental sulfur is easy to appear in the form of colloid, because the sulfur colloid can adsorb the sulfhydryl ions HS in the solution － And the surface of the sulfur micelle is adsorbed with a considerable amount of Fe by the adsorption of the micelle with negative charges 2+ Ion, fe 2+ Reacts with oxygen dissolved into the solution during stirring to generate Fe 3+ ：
4Fe 2+ +4H + +O 2 →4Fe 3+ +2H2O (9)
Fe produced 3+ Continuing to oxidize simple substance S into HSO 3－ 、H 2 SO 3 And a small amount of SO 3 2－ ：
S+4Fe 3+ +3H 2 O→H 2 SO 3 +4Fe 2+ +4H + (10)
H 2 SO 3 With O dissolved in the solution 2 The reaction generates SO again 4 2－ ：
2H 2 SO 3 +O 2 →2SO 4 2－ +4H + (11)
The following reactions occur in the reaction system between other substances in the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag:
MgO+H 2 SO 4 ＝MgSO 4 +H 2 O (12)
CaO+H 2 SO 4 ＝CaSO 4 +H 2 O (13)
Al 2 O 3 +H 2 SO 4 ＝Al 2 (SO 4 ) 3 +3H 2 O (14)
CuFeS 2 + O 2 + H + → Cu 2+ +So/-+S + Fe 2 O 3 ·H 2 O+ H 2 O (15)
the ferric ions hydrolyze to form hematite according to the following formula:
Fe 2 (SO 4 ) 3 + 3H 2 O ＝ Fe 2 O 3 + 3H 2 SO 4 (16)
the copper sulfide and copper ferrite react with sulfuric acid at normal temperature and pressure slowly, and in the leaching tank 5, the leaching agent is mainly an aqueous solution system of sulfuric acid, and except for water phase, part of O is brought by steam heating 2 And also plays a good role in oxidization. The leaching agent and the materials are simultaneously placed in a leaching tank 5 for stirring, the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag are synergistically leached by a heating strengthening means, sulfur is produced by elemental sulfur and sulfate radical, and S0 is completely eliminated in the leaching process 2 、H 2 S, NOX vapor emission, while also improving the co-leaching rate of Cu metal in both.
The copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag adopted by the application are used as synergistic leaching raw materials, so that the problems of high cost and high investment of single treatment of the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag are fundamentally solved. The leaching is carried out at the temperature of 80-90 ℃, and compared with the operation processes such as high-temperature roasting, oxygen pressure leaching, ammonia leaching and the like, the process operation safety is greatly improved while saving energy and environmental protection investment.
The leaching time is typically 6 hours. Stopping the operation when the leaching time reaches 6 hours, and feeding the leached mixed ore pulp into a thickener for concentration and liquid-solid separation by using a slurry pump.
The leaching residue contains iron, manganese, calcium, silicon and the like, and clear water with pH value of 6.5-7.5 under natural conditions is stirred and washed, and the washed slurry is fed into a filter press for filter pressing. The washing liquid is mixed with the leaching liquid and then fed into the next process, and the leaching residues are sent to a residue field for stacking.
The application discloses a method for cooperatively treating and recycling valuable metal copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag. The treatment method is suitable for treating low-grade copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag. The low-grade copper oxide concentrate leaching slag is subjected to flotation enrichment to obtain slag copper concentrate containing copper ferrous acid, copper ferrite, silicon pore brome, chalcanthite, trace copper blue, chalcanthite, chalcopyrite, blue chalcocite, enargite and other copper-containing substances, and the slag copper concentrate and copper sulfide concentrate calcine leaching slag are subjected to synergistic leaching to obtain good copper recovery rate. The high content of impurity elements such as calcium, iron, cadmium, manganese, phosphorus and the like does not influence the leaching of Cu metal in the co-leaching process of the two, and the leaching rate of main metal can reach more than 82 percent. Therefore, the comprehensive recovery of copper resources in the copper sulfide concentrate calcine slag and the copper oxide concentrate leaching slag can be realized.
The cooperative treatment method provided by the application has very wide application prospect in the hydrometallurgy field, and has the characteristics that the traditional process does not have:
(1) The low-grade copper oxide concentrate leaching slag can directly enter flotation under the condition of no need of ore grinding and pH adjustment, the flotation process is simple, the equipment investment is small, the grade of the slag copper concentrate after flotation is required to be 6-10%, and large investment is not needed in the actual treatment process.
(2) The synergistic leaching material composed of slag copper concentrate obtained after copper oxide concentrate leaching slag flotation and copper sulfide concentrate calcine leaching slag is simple to obtain, and consists of two single refractory materials which can be leached simultaneously in a sulfuric acid water solution system.
(3) The leaching process has simple material composition, no need of any other additives and oxidant, the high-temperature oxygen-enriched ions carried in the steam heating process can play a good role in oxidation, the three phases of gas, liquid and solid are uniformly mixed in the leaching tank 5, and the main oxide Fe which is rich in the leached slag is leached by the copper sulfide concentrate calcine 3+ Cu in the copper concentrate is selected from deoxidized leaching slag, so that the consumption of an oxidant and acid is reduced, and meanwhile, main metal copper in the oxidant and the acid is leached simultaneously.
(4) The synergistic leaching process is carried out in a closed container, the temperature is moderate, the stirring is moderate, and the improvement of mass transfer rate and the production control are facilitated.
(5) The synergistic leaching process is not caused by S, SO 2 、H 2 Environmental pollution question caused by S dischargeThe process flow is simple and clean.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Raw materials: copper concentrate (copper-containing 9.53%) is obtained by flotation and enrichment of leached slag (copper-containing 3.14%) of copper concentrate of a congo (gold) enterprise; copper sulfide concentrate calcine leaching slag (4.42% copper content).
Collecting copper oxide concentrate leaching slag containing 3.14% of copper, obtaining slag-separated copper concentrate containing 9.53% of copper, and copper sulfide concentrate calcine leaching slag containing 4.42% of copper, preparing mixed ore according to a ratio of 1:1, adding the mixed ore into a stirring tank with a model specification of 3 x 3.5m, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with a concentration of 2.55mol/L, adjusting the mass percentage concentration of ore pulp to be 15.19%, sending the ore pulp into a leaching tank 5, heating while stirring, keeping the temperature of the leaching tank 5 unchanged after the temperature reaches 85 ℃, and starting timing, wherein the leaching time is 6 hours.
After leaching, the mixed feed liquid enters the next flow through a discharge pump 8 to carry out subsequent treatments such as concentration filtration, and the subsequent treatments comprise: concentrating, separating and leaching the mixed feed liquid by a thickener to obtain leaching liquid and leaching slag, stirring and washing the leaching slag to obtain washing liquid and washing slag, discharging the tail of the washing slag, mixing the washing liquid and the leaching liquid, and performing electrodeposition in an extraction-back extraction process to prepare cathode copper; the raffinate obtained in the extraction step is subjected to an iron removal filtering step to obtain iron removal filtrate, the iron removal filtrate is subjected to a copper removal filtering step to obtain copper removal filtrate, and the copper removal filtrate is subjected to a cobalt precipitation step to prepare crude hydrogen cobalt oxide. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the synergistic leaching rate of copper in the slag copper concentrate and copper sulfide concentrate calcine leaching slag after flotation enrichment of 82.96%.
Example 2
Raw materials: copper concentrate (copper-bearing 6.93%) is obtained by flotation and enrichment of leached slag (copper-bearing 1.46%) of copper concentrate of a congo (gold) enterprise; copper sulfide concentrate calcine leaching residue (copper-containing 5.73%)
And (3) carrying out flotation enrichment on copper oxide concentrate leaching residues containing 1.46% of copper to obtain slag copper concentrate containing 6.93% of copper and copper sulfide concentrate calcine leaching residues containing 5.76% of copper, preparing mixed ores according to a ratio of 1:1, adding the mixed ores into a stirring tank with a model specification of 3 x 3.5m, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with a concentration of 2.04mol/L, adjusting the mass percentage concentration of ore pulp to be 15.49%, sending the ore pulp into a leaching tank 5, heating by introducing steam while stirring, and keeping the temperature of the leaching tank 5 unchanged after the temperature reaches 85 ℃, and starting timing, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the synergistic leaching rate of copper in the slag copper concentrate and copper sulfide concentrate calcine leaching slag after flotation enrichment, wherein the synergistic leaching rate is 82.78%.
Example 3
Raw materials: copper concentrate (copper-containing 7.02%) is obtained by flotation and enrichment of leached slag (copper-containing 2.06%) of copper concentrate of a congo (gold) enterprise; copper sulfide concentrate calcine leaching residue (containing 8.00% copper)
And (3) adding mixed ore prepared by flotation and enrichment of copper oxide concentrate leaching slag containing 2.06% of copper to obtain copper-containing 7.02% slag-selected copper concentrate and copper-containing 8.00% copper sulfide concentrate calcine leaching slag into a stirring tank with the model specification of 3 x 3.5m according to the proportion of 1:1, wherein the effective volume of the stirring tank is 21m < 3 >, adding sulfuric acid aqueous solution with the concentration of 2.11mol/L, adjusting the mass percentage concentration of ore pulp to be 16.67%, sending the ore pulp into a leaching tank 5, heating by introducing steam while stirring, and starting timing when the temperature of the leaching tank 5 is kept unchanged after the temperature reaches 85 ℃, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the synergistic leaching rate of copper in the slag copper concentrate and copper sulfide concentrate calcine leaching slag after flotation enrichment of 83.02%.
Example 4
Raw materials: copper concentrate (copper-containing 7.08%) is obtained by flotation and enrichment of leached slag (copper-containing 2.14%) of copper concentrate of a congo (gold) enterprise; copper sulfide concentrate calcine leaching residue (copper-containing 7.59%)
And (3) carrying out flotation enrichment on copper oxide concentrate leaching residues containing 2.14% of copper to obtain slag copper concentrate containing 7.08% of copper and copper sulfide concentrate calcine leaching residues containing 7.59% of copper, preparing mixed ores according to a ratio of 1:1, adding the mixed ores into a stirring tank with a model specification of 3 x 3.5m, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with a concentration of 2.08mol/L, adjusting the mass percentage concentration of ore pulp to be 16.01%, sending the ore pulp into a leaching tank 5, heating by introducing steam while stirring, and keeping the temperature of the leaching tank 5 unchanged after the temperature reaches 85 ℃, and starting timing, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the synergistic leaching rate of copper in the slag copper concentrate and copper sulfide concentrate calcine leaching slag after flotation enrichment of 82.99%.
Comparative example 1
Raw materials: in example 1, copper concentrate leaching residue (copper content 3.14%) of a congo (gold) ore rabbet, copper sulfide concentrate calcine leaching residue (copper content 4.42%) were taken.
Adding mixed ore prepared from copper oxide concentrate leaching slag containing 2.75% of copper and copper sulfide concentrate calcine leaching slag containing 4.42% of copper into a stirring tank with the model specification of 3 x 3.5m according to the proportion of 1:1, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with the concentration of 2.55mol/L, adjusting the mass percentage concentration of ore pulp to be 15.19%, sending the ore pulp into a leaching tank 5, stirring while introducing steam for heating, keeping the temperature of the leaching tank 5 unchanged after the temperature reaches 85 ℃, and starting timing, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the synergistic leaching rate of copper in the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag which is 71.54%.
Comparative example 2
Raw materials: taking slag copper concentrate (9.53% copper) obtained by flotation and enrichment of copper concentrate leaching slag (3.14% copper) of Congo (gold) ore rabbet copper oxide concentrate in example 1
And (3) carrying out flotation enrichment on copper oxide concentrate leaching residues containing 3.14% of copper to obtain slag copper concentrate containing 9.53% of copper, adding the slag copper concentrate roasting leaching residues into a stirring tank with the model specification of 3 x 3.5m, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with the concentration of 2.18mol/L, adjusting the mass percentage concentration of ore pulp to be 16.01%, sending the ore pulp into a leaching tank 5, stirring and introducing steam to heat, keeping the temperature of the leaching tank 5 unchanged after the temperature reaches 85 ℃, and starting timing, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the single leaching rate of the slag-copper concentrate of 55.76%.
Comparative example 3
Raw materials: copper sulfide concentrate calcine leaching residue (containing 4.42% of copper) of congo (gold) ore enterprise
Adding the copper concentrate which contains copper and is 4.42% of copper concentrate calcine leaching slag and is not added with slag which is enriched by floatation into a stirring tank with the model specification of 3 x 3.5m, taking 21m3 of the effective volume of the stirring tank, adding sulfuric acid aqueous solution with the concentration of 2.18mol/L, adjusting the mass percentage concentration of ore pulp to be 16.01%, sending the ore pulp into a leaching tank 5, stirring and heating by steam, and keeping the temperature of the leaching tank 5 unchanged and starting timing after the temperature reaches 85 ℃, wherein the leaching time is 6 hours.
After the leaching is finished, the mixed liquid enters the next flow through a discharge pump 8 to be subjected to subsequent treatments such as concentration and filtration, and the subsequent treatments are the same as in example 1. And measuring the total copper content in the leached washing slag by using an atomic absorption spectrometer, and calculating to obtain the single leaching rate of the leached slag of the roasted copper sulfide concentrate, wherein the single leaching rate is 40.72%.
While the application has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the application, and in particular, the technical features set forth in the various embodiments may be combined in any manner so long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The method for synchronously recovering the metal copper in the copper oxide concentrate leaching slag and the copper sulfide concentrate calcine leaching slag is characterized in that the Cu grade of the copper oxide concentrate leaching slag is 1-3%, and the Cu grade of the copper sulfide concentrate calcine leaching slag is 4-8%, and the method comprises the following steps:
(1) Carrying out acid flotation on the copper oxide concentrate leaching slag to obtain slag-separated copper concentrate with Cu grade of 6-10%;
(2) The obtained slag copper concentrate and copper sulfide concentrate calcine leaching slag are subjected to slag separation according to the mass ratio of 1: mixing the materials according to the proportion of (1-1.2) to obtain mixed ore;
(3) Stirring and mixing the obtained mixed ore and a leaching agent to obtain slurry, wherein the leaching agent is a sulfuric acid solution system leaching agent; the mass concentration of the slurry is 15-17%;
(4) Leaching the obtained slurry at 80-90 ℃ and carrying out solid-liquid separation to obtain leaching residues and leaching liquid;
(5) Washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching solution to obtain a loaded organic phase and a raffinate, wherein the obtained washing liquid is used in the extraction step, and the obtained washing slag is subjected to tail removal treatment; the raffinate obtained by extraction is used for preparing the sulfuric acid solution system leaching agent;
(6) And carrying out back extraction and electrodeposition on the obtained loaded organic phase to obtain the metallic copper.
2. The method for synchronously recovering metallic copper in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 1, wherein the acidic flotation of the copper oxide concentrate leaching residue in the step (1) comprises the following steps:
(a) Mixing the copper oxide concentrate leaching slag with water to obtain ore pulp, wherein the mass percentage concentration of the ore pulp is 15-25%;
(b) Adding a collector and a foaming agent into the obtained ore pulp for roughing to obtain rough concentrate and roughing tailings;
(c) Carrying out first concentration and second concentration on the obtained rough concentrate to obtain slag-separated copper concentrate; scavenging the obtained roughing tailings to obtain copper scavenging middlings and tailings, wherein the copper scavenging middlings enter a first concentration step, and the tailings are subjected to tailing discharge.
3. The method for synchronously recycling copper metal in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 2, wherein the collector in the step (b) is dithiocarbonic acid-O-butyl sodium salt, and the adding amount is 100-300 g/ton of copper oxide concentrate leaching residue.
4. The method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag according to claim 2, wherein the foaming agent in the step (b) is pine oil, and the addition amount is 30-50 g/ton of copper oxide concentrate leaching slag.
5. The method for synchronously recovering metallic copper in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 2, wherein the first concentrating in step (c) produces copper middling and copper concentrate, the copper middling returning to the roughing step; the copper concentrate enters a second beneficiation.
6. The method for synchronously recovering metallic copper in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 2, wherein the second concentration in the step (c) produces copper middling second and slag copper concentrate, the copper middling second returns to the first concentration step, and the slag copper concentrate is slag copper concentrate with a Cu grade of 6-10%.
7. The method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag according to claim 1, wherein the particles with the particle size of less than 0.074mm in the slurry in the step (3) account for 70-80% of the total particle weight.
8. The method for synchronously recovering metallic copper in copper oxide concentrate leaching slag and copper sulfide concentrate calcine leaching slag according to claim 1, wherein the leaching time of the slurry obtained by leaching at 80-90 ℃ in the step (4) is more than 6 hours.
9. The method for synchronously recovering metallic copper in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 1, wherein the step (4) further comprises concentrating the leached slurry before solid-liquid separation.
10. The method for synchronously recovering metallic copper in copper oxide concentrate leaching residue and copper sulfide concentrate calcine leaching residue according to claim 1, wherein the washing of the obtained leaching residue in the step (5) comprises stirring and washing the obtained leaching residue with clear water with a pH of 6.5-7.5 under natural conditions.
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