CN112609082A - Method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid - Google Patents
Method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid Download PDFInfo
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- CN112609082A CN112609082A CN202011372288.7A CN202011372288A CN112609082A CN 112609082 A CN112609082 A CN 112609082A CN 202011372288 A CN202011372288 A CN 202011372288A CN 112609082 A CN112609082 A CN 112609082A
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- copper
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- 239000010949 copper Substances 0.000 title claims abstract description 281
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 110
- 239000007788 liquid Substances 0.000 title claims abstract description 108
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 239000004071 soot Substances 0.000 title claims abstract description 79
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 227
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000000605 extraction Methods 0.000 claims abstract description 69
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 141
- 230000008569 process Effects 0.000 claims description 53
- 239000011701 zinc Substances 0.000 claims description 52
- 229910052725 zinc Inorganic materials 0.000 claims description 49
- 238000001914 filtration Methods 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 43
- 238000005406 washing Methods 0.000 claims description 43
- 239000012074 organic phase Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 229910052785 arsenic Inorganic materials 0.000 claims description 32
- 229910052709 silver Inorganic materials 0.000 claims description 32
- 239000004332 silver Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052797 bismuth Inorganic materials 0.000 claims description 28
- 150000002739 metals Chemical class 0.000 claims description 28
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 27
- 238000007654 immersion Methods 0.000 claims description 25
- 238000003723 Smelting Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 230000001698 pyrogenic effect Effects 0.000 claims description 9
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 9
- 238000001471 micro-filtration Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- -1 silver metals Chemical class 0.000 claims description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 6
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000011133 lead Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- 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
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, which takes the copper-containing soot and the acidic waste liquid as leaching raw materials and comprises the steps of middle leaching treatment, low leaching liquid and partial copper raffinate as bottom water, and middle leaching liquid and middle leaching residues; secondary low leaching treatment, copper extraction treatment and copper electrolysis to prepare low leaching solution and low leaching residue; the leaching cost is reduced, the synergistic treatment of the acidic waste liquid and the copper-containing soot is realized, and the cathode copper plate with the copper content of more than 99.99 percent is prepared. The purpose of recycling the waste is achieved, and the production and preparation cost is reduced.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy and comprehensive utilization of resources, and particularly relates to a method for preparing high-purity cathode copper by cooperatively treating copper-containing soot and acidic waste liquid, in particular to a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid.
Background
Nonferrous metals such as copper, zinc, lead and the like are important basic materials for national economy, social development and construction, and copper is a metal which is very closely important to human. Copper has good heat-conducting property and strong ductility and corrosion resistance, so the copper is an indispensable raw material in the industries of light industry, mechanical manufacturing, transportation, electronics, building, military industry and the like. At present, more than about 80% of mineral copper is produced by carrying out a pyrometallurgical smelting process on copper sulfide concentrate, namely, the copper concentrate is smelted by matte making to produce copper matte, the copper matte is blown and refined by a converter and a pyrometallurgy to produce anode copper, and the anode copper is electrolytically refined in a sulfuric acid system to produce cathode copper. During the copper pyrometallurgy process, smoke and dust are produced under the action of volatilization and air flow, and the copper soot is obtained after cooling and dust collection. Copper soot has different components depending on the conditions of ore composition, smelting process, dust collecting equipment, etc., but generally contains Cu, Zn, Pb, Cd, Bi, etc. For the treatment of the substances, domestic enterprises return the substances to a smelting furnace for smelting, and the consequence is that the treatment capacity of the smelting furnace is reduced and harmful elements are accumulated to reduce the product purity. Therefore, it is necessary to perform an open-circuit treatment of the copper soot. On the premise of comprehensively considering various factors such as valuable metal resource recovery, environmental protection and the like, the copper soot at home and abroad mainly comprises a blast furnace smelting method, a combined fire-wet method and a full-wet method treatment process at present. The blast furnace smelting method and the fire-wet method combined method have the problems of high energy consumption, large environmental pollution, high production cost, low product recovery rate and the like. The full-wet treatment process has less environmental pollution, is most widely and mature in industrial application at present, most commonly adopts a sulfuric acid system to leach valuable metals such as copper, zinc and the like into leaching liquid, lead, bismuth and the like into leaching slag, and finally obtains a product by separation through methods such as extraction, chemical precipitation and the like. However, the process is still not complete enough, and has the defects of large acid consumption, low leaching rate of part of valuable metals, poor metal separation effect and the like, so the economic and efficient copper soot treatment process is still a problem to be solved urgently at present.
The waste sulfuric acid is a waste liquid containing a large amount of free acid, iron (mostly divalent) and other trace heavy metal elements, which is generated in the fields of organic chemical industry enterprise production, electronic component cleaning, surface oxide cleaning by machining and the like, the environment can be seriously damaged due to high pollution, and the treatment method mainly adopts lime, liquid alkali and the like for acid-base neutralization. The waste acidic etching solution is waste liquid generated in the PCB etching process, and the main component of the waste acidic etching solution is CuCl2、 HCl、NH4Cl and the like have great environmental pollution, and the treatment method mostly adopts alkali for neutralization and then uses sulfuric acid for neutralization to recover copper sulfate products. The two acidic waste treatment processes consume a large amount of alkali, generate a large amount of sludge and easily cause secondary pollution. Besides heavy metal elements, the two types of wastes also contain free acid with greater comprehensive utilization value, and greater economic and environmental benefits can be generated if the wastes can be reasonably recycled. For example, Chinese patent publication No. CN 105950874B entitled "method for combined treatment of copper smelting soot and contaminated acid". The method comprises the steps of mixing copper smelting soot and waste acid raw materials, adding an oxidant to control potential oxidation leaching after mixing and pulping the copper smelting soot and the waste acid, dissolving metals such As copper, arsenic and zinc in the copper soot into a leaching solution, precipitating metals such As lead and bismuth into leaching slag, adding the oxidant into the leaching solution to completely oxidize As (III) in the solution into As (V), adding sodium sulfide to precipitate copper in the solution in the form of copper sulfide to produce copper concentrate, adding a reducing agent into the solution after copper removal to completely reduce As (V) in the solution into As (III), then adding sodium sulfide to precipitate arsenic in the form of arsenic sulfide in the solution, and finally neutralizing the solution after arsenic removal with alkali to discharge after reaching the standard. With simultaneous application of oxygen at controlled potentialChemical leaching, potential-controlled oxidation vulcanization and reduction vulcanization are combined to separate and recover valuable metals in copper smelting soot and waste acid step by step, so that cyclic utilization of waste in a system is realized, and the purpose of treating waste by waste is achieved. However, the process has long flow, and the treatment of waste acid and other metal elements is difficult, so the treatment cost is higher.
Also, for example, Chinese patent publication No. CN 105567983B, "a soot treatment process in copper smelting process". Provides a soot treatment process in a copper smelting process, which comprises the following steps: firstly, leaching copper smelting soot by water to obtain a water leaching solution and water leaching slag; then, performing acid leaching on one part of the water leaching residue obtained in the step to obtain acid leaching solution, and performing alkali leaching on the other part of the water leaching residue to obtain alkali leaching solution; then carrying out metal replacement copper precipitation on the pickle liquor obtained in the step to obtain a filtrate after copper precipitation; and finally, neutralizing and oxidizing the filtrate obtained after copper precipitation and the alkaline leaching solution obtained in the step to obtain ferric arsenate precipitate and filtrate after arsenic precipitation. The soot treatment process provided by the invention is especially directed at a high-arsenic and high-copper soot treatment process, the problem of harmless treatment of arsenic in high-arsenic and high-copper soot is solved through the process, and meanwhile, valuable metals such as copper and zinc in the high-arsenic and high-copper soot are comprehensively recovered, so that gradient recovery and comprehensive utilization of soot impurities are realized. But the raw materials are mainly treated aiming at the high-arsenic and high-copper smoke dust raw materials.
Chinese patent CN103643044B "A direct extraction technology of copper and zinc from copper ash by wet process"; the process is a process for directly extracting copper and zinc from copper ash by a wet method, and is used for efficiently treating low-grade copper ash materials. The process flow comprises the following steps: leaching → organic removal → copper extraction → iron removal, aluminum, chromium → zinc extraction → zinc-free solution back leaching (open circuit 20-30%). The direct extraction operation process is adopted, so that more low-grade copper ash can be recycled, low-grade high-impurity ash materials generated by pyrometallurgical crude copper which is difficult to process at present can be processed, and valuable metals of low-grade copper-zinc ash can be recycled more thoroughly. However, the copper content of the copper to be treated has the problem of continuous purification and the like. I.e. further purification of the extracted copper is required. Chinese patent publication No. CN106011488B discloses a method for comprehensively recovering valuable metals from high-arsenic copper soot. The invention discloses a method for comprehensively recovering valuable metals from high-arsenic copper soot, which uses arsenic-containing copper soot as a raw material, firstly adopts an alkaline leaching process to convert arsenic, tin and zinc into oxysalt to enter a solution, then cools and crystallizes to separate out sodium arsenate crystals, zinc and tin are sulfide-precipitated from obtained mother liquor, and the alkaline leaching residue realizes the separation and recovery of copper, indium, bismuth and lead by a sulfuric acid leaching step-by-step extraction process, wherein the removal rate of arsenic is more than 95% and the recovery rates of copper, indium, zinc and tin are more than 90% in the metal separation and recovery process. The method can remove arsenic efficiently from the source, has the characteristics of good adaptability to raw materials, simple operation, high efficiency, cleanness, low energy consumption, high metal recovery rate and the like, and has remarkable economic and social benefits. The same is also the treatment process for the copper ash raw material with high arsenic content.
The Chinese patent publication No. CN 103643044A discloses a wet direct copper and zinc extraction process for copper ash, and the recovery method is a wet direct copper and zinc extraction process for copper ash, which efficiently treats low-grade copper ash materials. The process flow of the invention is as follows: leaching → removing organic → extracting copper → removing iron, aluminum, chromium → extracting zinc → leaching without zinc solution (open circuit 20-30%). The invention adopts the direct extraction operation process, can recycle more low-grade copper soot, reduces the total amount of environmental wastes, has high product conversion rate, high product added value, low cost, energy conservation and environmental protection, can treat the soot material with low grade and high impurity generated by pyrometallurgical crude copper which is difficult to treat at present, and can more thoroughly recycle the valuable metals of the low-grade copper zinc soot.
As can be seen from the above patent and literature scope, the above literature reports on the recovery of valuable metals Cu and Zn by treating copper-containing soot by the all-wet process, and the literature reports on the combined treatment of copper soot and waste acid. However, for the method for preparing high-purity cathode copper by adopting synergistic treatment of copper-containing soot and acidic waste liquid, and adopting multi-level medium circulation and solution open circuit in the process, the consumption of auxiliary materials in the leaching, extraction and electrolysis processes is reduced, and the impurity content in the cathode copper product is effectively reduced, and the same report is not found in the prior art documents.
Compared with the traditional copper concentrate, the existing full-wet process for treating the copper-containing soot auxiliary material has the advantages of high consumption, low leaching rate and low quality of the recovered product.
Therefore, how to provide a technical process method for preparing high-purity cathode copper by cooperatively treating copper-containing soot and acidic waste liquid aims at the problems that the conventional full-wet method copper-containing soot treatment process is high in auxiliary material consumption, low in leaching rate and low in quality of recovered products, and the conventional acidic waste liquid treatment process is high in alkali liquor consumption and generates a large amount of sludge, so that secondary pollution is easily caused. Meanwhile, according to respective physicochemical properties of the copper-containing soot and the acidic waste liquid, a method for preparing high-purity cathode copper by cooperatively treating the copper-containing soot and the acidic waste liquid is provided, so that the heavy metal in the copper-containing soot is dissolved out by fully utilizing free acid in the acidic waste liquid, and the preparation of the high-purity cathode copper is realized by applying extraction-electrodeposition, so that the low-cost comprehensive utilization of the copper-containing soot and the acidic waste liquid is realized, and the process method has the characteristics of high metal recovery rate, small environmental pollution, simple process and high recovered product quality; has important practical significance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, wherein the copper-containing soot and the acidic waste liquid are used as leaching raw materials, the method comprises the steps of middle leaching treatment, low leaching solution and part of copper raffinate are used as bottom water, and the middle leaching solution and middle leaching residues; performing secondary low leaching treatment to prepare low leaching solution and low leaching residue; the leaching cost is reduced, the synergistic treatment of the acidic waste liquid and the copper-containing soot is realized, and the cathode copper plate with the copper content of more than 99.99 percent is prepared. The purpose of recycling the waste is achieved, and the production and preparation cost is reduced.
The invention discloses a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, which takes the copper-containing soot and the acidic waste liquid as leaching raw materials and comprises the following steps:
1) and (3) middle leaching treatment:
taking low-leaching solution and part of copper raffinate as bottom water, firstly carrying out size mixing on the copper-containing soot and the acidic waste liquid to obtain size mixing solution, then carrying out primary leaching treatment on the size mixing solution and the bottom water for several hours, and carrying out precipitation, filtration and solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver metals;
2) and the second low leaching treatment is carried out,
mixing rainwater, ground washing water and recycled water after sewage treatment serving as secondary low-leaching bottom water and middle leaching residues for size mixing treatment to obtain middle leaching residue mixed solution, adding waste sulfuric acid and a low-leaching oxidant into the middle leaching residue mixed solution for secondary low leaching treatment, and filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residues;
3) copper extraction treatment and copper electrolysis,
finely filtering the intermediate leaching solution obtained in the step 1) to obtain a finely filtered solution, adding a copper extractant to perform Cu extraction to obtain raffinate, and recovering valuable metals Zn and As from the raffinate; washing with water, performing back extraction treatment and enrichment treatment to obtain a copper-rich solution;
deoiling the copper-rich solution after back extraction to obtain electrolyte, pumping into an electrolytic bath, electrolyzing with an anode made of lead-calcium-strontium-silver quaternary alloy and a copper plate as a cathode, and controlling the voltage and current density of the electrolytic bath to 150A/m2-200 A/m2And the same polar distance is 70mm-90mm, and a cathode copper plate with the copper content of more than 99.99 percent is prepared.
The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid comprises the step 1) of leaching treatment, wherein the process conditions are that the acidic waste liquid and the copper soot are controlled according to a liquid-solid ratio, and the ratio of the liquid volume L to the solid weight Kg is 5-7: 1, preparing a size mixing liquid; controlling the pH of the solution to be 2.0-3.0 during the middle leaching treatment, and adding the materials while stirring for 60-120min under the condition of continuous stirring; filtering and carrying out solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver; detecting the Cu content in the middle immersion liquid and the middle immersion slag, and controlling the Cu content in the middle immersion liquid to be 10-20 g/L; and (4) smelting the middle leaching slag by a pyrogenic process to recover lead, bismuth and silver. Preferably, the secondary low leaching treatment in the step 2) is carried out by controlling the liquid-solid ratio of secondary low leaching bottom water to middle leaching residue to be 3-5: 1, controlling the secondary low leaching temperature to be 50-60 ℃, and controlling the mass ratio of the low leaching oxidant to Cu in the middle leaching residue to be 0.5-0.7; controlling the acid concentration of the solution to reach 0.3-0.6mol/L in the secondary low leaching treatment, continuously stirring for 30-60min under the condition, finally filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residue enriched with lead, bismuth and silver, and sending the obtained enriched leaching residue to a pyrogenic process again for smelting and recovering lead, bismuth and silver; the low-leaching solution is returned to the step 1) for leaching the treated bottom water.
The method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid comprises the following steps of 3) copper extraction treatment and copper electrolysis:
A. filtering, namely performing precise filtration treatment on the intermediate leaching solution in the step 1) to obtain a precise filtration dissolving solution;
B. adding a Cu extracting agent into the precision filtration dissolving solution, and carrying out Cu extraction treatment to obtain raffinate and a copper-containing organic phase; controlling Cu in the raffinate to be less than or equal to 1.0 g/L;
C. recovering the valuable metals Zn and As, namely, allowing the raffinate which is prepared in the previous step and has the mass ratio of 55-65% to enter a Zn and As valuable metal recovery process section to recover the valuable metals Zn and As, and taking the rest of the raffinate which enters the recovery process section As the middle leaching bottom water in the step 1);
D. washing, namely sending the copper-containing organic phase to a washing section for washing, taking a precision filtration dissolving solution as a water phase, and controlling the concentration of a washing acid solution during washing; controlling the flow ratio of the water phase to the organic phase to be 1:40-50, feeding the water-washed organic phase obtained after water washing to a back extraction section, and obtaining a copper-rich solution after back extraction;
E. and (3) electrolyzing, namely deoiling the copper-rich solution subjected to back extraction, pumping the copper-rich solution into an electrolytic bath, and preparing a cathode copper plate with the copper content of more than 99.99% by using a lead-calcium-strontium-silver quaternary alloy as an anode and a copper plate as a cathode.
Preferably, the low-leaching oxidant is sodium chlorate or sodium sulfate.
According to the method for preparing the high-purity cathode copper by using the copper-containing soot and the acidic waste liquid, the solid content in the solution subjected to precise filtration is controlled to be less than 0.03 g/L.
In the method for preparing the high-purity cathode copper by using the copper-containing soot and the acidic waste liquid, in the step B, the Cu extraction is that M5640 or LiX98 is used as an extracting agent and is mixed with No. 260 kerosene to be an organic phase, and the extracting agent is controlled to be as follows: and (2) taking the fine filtration dissolving solution as a water phase, controlling the flow ratio of the water phase to an organic phase to be 1:2-4, and performing Cu extraction on the 260# kerosene under the condition of 10-25: 90-75.
The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid comprises the step D of washing with water, wherein the concentration of a washing acid solution is controlled to be 0.08-0.12N, the concentration of Cu is controlled to be 25-40g/L, and H is controlled+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 2.0-2.5N is used as stripping acid, and the ratio of the stripping acid to the organic phase flow containing copper is controlled to be 1:3-4, obtaining Cu concentration of 45-55g/L, H+Is a copper-rich solution of 1.5-2.0N.
The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid comprises the step E of electrolysis, wherein the voltage of a cell is controlled to be 1.7V-2.1V, and the current density is controlled to be 150A/m2-200 A/m2(ii) a And simultaneously periodically measuring the concentration of impurity ions in the electrolyte in the electrolytic cell, when the following ion concentrations in the electrolyte satisfy one of the following conditions: c (Cl-) > 0.3g/L, c (As) > 0.5g/L, c (Sb) > 0.2g/L, c (Bi) > 0.5g/L, and 3-6% of electrolyte in the electrolytic bath is used As the bottom water in the step 1); the cathode copper plate with the copper content of more than 99.99 percent is prepared.
The invention discloses a method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution, which mainly comprises the following production process: copper soot, acidic waste liquid → middle leaching treatment → middle leaching solution → extraction, raffinate recovery → copper-containing organic phase → washing → electrowinning barren solution, stripping → copper stripping solution → electrolysis → cathode copper. Middle immersion liquid → secondary low immersion, low immersion liquid recovery → low immersion slag → recovery of lead, bismuth and silver.
The invention discloses a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, which is characterized by comprising the following steps of:
according to the invention, the acidic waste liquid is used as a leaching reagent, so that the leaching cost is reduced, the synergistic treatment of the acidic waste liquid and the copper-containing ash is realized, the copper plate with the copper content of more than 99.99% is obtained, and the high-valued utilization of hazardous waste resources is realized through medium circulation and waste comprehensive utilization, so that the purpose of making waste from waste is achieved;
and in the middle leaching stage, the low leaching solution and part of copper raffinate are used as bottom water, and in the low leaching stage, reuse water is used as bottom water, so that water resources and the use amount of sulfuric acid are saved. Meanwhile, through two-stage leaching, the leaching rate of the copper and the zinc is more than 98.5 percent and more than 99.0 percent, and the entrainment of the copper and the zinc in the leaching slag is reduced; meanwhile, in the extraction stage, the raffinate is opened to a zinc extraction line to recover valuable metal elements such As Zn, As and the like, so that the comprehensive recovery of valuable metal resources is realized, the resource waste is avoided, and the method is economical and environment-friendly;
thirdly, the electrolytic copper barren solution is circulated to a back extraction stage to be used as back extraction acid, so that the consumption of the extraction acid is effectively reduced, and the extraction cost is reduced. Meanwhile, the impurity content in the cathode copper product is effectively reduced through the open circuit of the electrolyte, and the product quality is improved. The method has the advantages of simple process, strong raw material applicability, low labor intensity, low production cost and the like, and is easy for industrial popularization.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, wherein the meaning of the low-leaching or the second low-leaching is the same, and the meaning of the microfiltration dissolution liquid or the microfiltration dissolution liquid is the same, and the ratios of the respective components are mass ratios in the following embodiments unless otherwise specified.
The invention discloses a method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, which takes the copper-containing soot and the acidic waste liquid as leaching raw materials and comprises the following steps:
1) and (3) middle leaching treatment:
taking low-leaching solution and part of copper raffinate as bottom water, firstly carrying out size mixing on the copper-containing soot and the acidic waste liquid to obtain size mixing solution, then carrying out primary leaching treatment on the size mixing solution and the bottom water for several hours, and carrying out precipitation, filtration and solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver metals; the process conditions are that the ratio of the volume L of the liquid to the weight Kg of the solid is 5-7: 1, preparing a size mixing liquid; controlling the pH of the solution to be 2.0-3.0 during the leaching treatment, adding the materials while stirring for 60-120min under the condition of continuous stirring; filtering and carrying out solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver; detecting the Cu content in the middle immersion liquid and the middle immersion slag, and controlling the Cu content in the middle immersion liquid to be 10-20 g/L; smelting the middle leaching slag by a pyrogenic process to recover lead, bismuth and silver;
2) and the second low leaching treatment is carried out,
mixing rainwater, ground flushing water and recycled water after sewage treatment serving as secondary low-leaching bottom water and middle leaching residues for size mixing treatment to obtain middle leaching residue mixed solution, adding waste sulfuric acid and a low-leaching oxidant into the middle leaching residue mixed solution, performing secondary low-leaching treatment by using the low-leaching oxidant which is sodium chlorate or sodium sulfate, and filtering and performing solid-liquid separation to obtain low-leaching solution and low-leaching residues; specifically, the liquid-solid ratio of secondary low-leaching bottom water to middle-leaching residue is controlled to be 3-5: 1, controlling the leaching temperature to be 50-60 ℃, and controlling the mass ratio of the low-leaching oxidant to Cu in the middle leaching residue to be 0.5-0.7; controlling the acid concentration of the solution to reach 0.3-0.6mol/L in the secondary low leaching treatment, continuously stirring for 30-60min under the condition, finally filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residue rich in lead, bismuth and silver, and sending the obtained rich leaching residue to a pyrogenic process again for smelting and recovering the lead, bismuth and silver; returning the low-leaching solution to the step 1) for leaching the bottom water;
3) copper extraction treatment and copper electrolysis,
performing precision filtration on the medium immersion liquid in the step 1) to obtain precision filtration dissolving liquid, and controlling the solid content in the precision filtration dissolving liquid to be less than 0.03 g/L; adding a copper extractant to carry out Cu extraction to obtain raffinate, and recovering valuable metals Zn and As from the raffinate; washing with water, performing back extraction treatment and enrichment treatment to obtain a copper-rich solution;
deoiling the copper-rich solution after back extraction to obtain electrolyte, pumping into an electrolytic bath, electrolyzing with an anode made of lead-calcium-strontium-silver quaternary alloy and a copper plate as a cathode, and controlling the voltage and current density of the electrolytic bath to 150A/m2-200 A/m2And the same polar distance is 70mm-90mm, and a cathode copper plate with the copper content of more than 99.99 percent is prepared.
Step 3) copper extraction treatment and copper electrolysis, comprising the following steps:
A. filtering, namely performing precise filtration treatment on the primary leaching solution obtained in the step 1) to obtain a precise filtration dissolving solution; controlling the solid content in the solution of the microfiltration solution to be less than 0.03 g/L.
B. Adding a Cu extracting agent into the microfiltration dissolved solution, wherein M5640 or LiX98 is used as the extracting agent, and the Cu extracting agent is mixed with No. 260 kerosene to form an organic phase, and controlling the content of the extracting agent: the method comprises the following steps of (1) taking No. 260 kerosene 10-25:90-75, taking a precision filtration dissolving solution as a water phase, controlling the flow ratio of the water phase to an organic phase to be 1:2-4, and carrying out Cu extraction treatment by Cu extraction to obtain raffinate and a copper-containing organic phase; controlling Cu in the raffinate to be less than or equal to 1.0 g/L;
C. recovering the valuable metals Zn and As, namely, allowing the raffinate which is prepared in the previous step and has the mass ratio of 55-65% to enter a Zn and As valuable metal recovery process section to recover the valuable metals Zn and As, and taking the rest of the raffinate which enters the recovery process section As the middle leaching bottom water in the step 1);
D. washing, namely sending the copper-containing organic phase to a washing section for washing, taking a precision filtration dissolving solution as a water phase, and controlling the concentration of a washing acid solution during washing; controlling the flow ratio of the water phase to the organic phase to be 1:40-50, feeding the water-washed organic phase obtained after water washing to a back extraction section, and obtaining a copper-rich solution after back extraction; controlling the concentration of the acid washing solution to be 0.08-0.12N, the concentration of Cu to be 25-40g/L and H+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 2.0-2.5N is used as stripping acid, and the ratio of the stripping acid to the organic phase flow containing copper is controlled to be 1:3-4, obtaining Cu concentration of 45-55g/L, H+Is a copper-rich solution of 1.5-2.0N.
E. Electrolyzing, deoiling the copper-rich solution after back extraction, pumping into an electrolytic bath, adopting a lead-calcium-strontium-silver quaternary alloy as an anode, a copper plate as a cathode, controlling the bath voltage to be 1.7V-2.1V and the current density to be 150A/m2-200 A/m2The same polar distance is 70mm-90 mm; and simultaneously periodically measuring the concentration of impurity ions in the electrolyte in the electrolytic cell, when the following ion concentrations in the electrolyte satisfy one of the following conditions: c (Cl-) is not less than 0.3g/L, c (As)
0.5g/L, c (Sb) is more than or equal to 0.2g/L, c (Bi) is more than or equal to 0.5g/L, and 3-6% of electrolyte in the electrolytic bath is used as bottom water in the step 1); preparing a cathode copper plate with the copper content of more than 99.99 percent; the cathode copper plate with the copper content of more than 99.99 percent is prepared.
The following examples are the same as the above-described embodiments except for the following descriptions.
Example 1
The raw material components used in the examples of the present invention are shown in the following table;
copper-containing soot principal constituent table units: is based on
| Zn | Pb | Cu | Sn | Cd | Fe | Cl | As | Water content |
| 18.29 | 6.72 | 5.27 | 2.47 | 0.04 | 0.7 | 12.92 | 0.1 | 27.24 |
The main components of the waste sulfuric acid are shown in the table unit: g/L
| SO4 2- | Na | Mg | Ca | Al | Fe2+ |
| 385.6 | 0.52 | 0.29 | 0.14 | 0.21 | 15.3 |
Description of the drawings: the copper soot and the waste acid are used as raw materials, and the waste acid is a waste sulfuric acid solution as a main component. 1) The middle leaching treatment is carried out to obtain the intermediate leaching solution,
taking the low-leaching solution and part of copper raffinate as bottom water, pulping the copper-containing soot and the acidic waste liquid, leaching for the first time, allowing part of copper and most of zinc and cadmium to enter the leaching solution, and allowing metals such as lead, bismuth and the like to precipitate and enter leaching residues. The technical conditions of the intermediate leaching are as follows: mixing the acidic waste liquid and the ash according to a liquid-solid ratio (the ratio of the liquid volume L to the solid weight Kg) of 5: 1-7: 1, controlling the pH value to be kept at 2.0-3.0 in the process, after the feeding is finished, keeping the pH value stable and continuing to stir at 2.0-3.0 for 60-120min, carrying out solid-liquid separation to obtain a middle immersion liquid and middle immersion slag containing valuable metals such as lead, detecting the Cu content in the middle immersion liquid and the middle immersion slag, and keeping the copper content in the middle immersion liquid at 10-20 g/L;
2) the secondary low leaching treatment is carried out,
taking initial rainwater, ground washing water, reuse water after sewage treatment and the like as bottom water, adding waste sulfuric acid after size mixing of middle leaching residues, adding an oxidant sodium chlorate for secondary leaching, leaving lead, bismuth and silver in leaching residues, sending the obtained enriched leaching residues to a pyrogenic process for smelting and recovering lead, bismuth and silver, and returning low-leaching solution to middle leaching to be used as bottom water. The technical conditions of low leaching are as follows: the liquid-solid ratio of the bottom water to the middle leaching residue is 3: 1-5: 1, the leaching temperature is 50-60 ℃, the mass ratio of sodium chlorate to Cu in the middle leaching residue is 0.5-0.7, when the acidity reaches 0.3-0.6mol/L and is kept stable, stirring is continued for 30-60min, and then solid-liquid separation is carried out to obtain low leaching liquid and low leaching residue;
3) copper extraction treatment and copper electrolysis
And (3) carrying out precision filtration on the medium immersion liquid in the step 1), controlling the solid content in the filtrate to be less than 0.03g/L, and then conveying the filtrate to an extraction section. The Cu extraction is preferably carried out by mixing extracting agents M5640 and 260# kerosene into an organic phase, wherein the extracting agents are as follows: and (2) when the No. 260 kerosene is 10-25:90-75, taking the dissolving solution As a water phase, controlling the flow ratio of the water phase to an organic phase to be 1:2-4, carrying out Cu extraction to obtain raffinate, controlling Cu in the raffinate to be less than or equal to 1.0g/L, opening 60% of the raffinate to a zinc extraction production line to recover valuable metals such As Zn and As, and opening the rest raffinate to be used As middle leaching bottom water. Sending the copper-containing organic phase to a water washing section for washing, and controlling the flow ratio of the water phase to the organic phase to be 1:40-50 and the concentration of washing acid to be 0.1N; after washing, the organic phase is sent to a back extraction section, sulfuric acid-copper sulfate electrobarren solution with the Cu concentration of 25-40g/L and the H + of 2.0-2.5N is used as back extraction acid, the flow ratio of the back extraction acid to the loaded organic phase is controlled to be 1:3-4, and copper-rich solution with the Cu concentration of 45-55g/L, H + of 1.5-2.0N is obtained;
and deoiling the copper-rich solution after back extraction, pumping the copper-rich solution into an electrolytic cell, wherein an anode made of a lead-calcium-strontium-silver quaternary alloy is adopted during electrolysis, a copper plate is used as a cathode, the cell voltage is 1.7V-2.1V, the current density is 150A/m 2-200A/m 2, and the same polar distance is 70mm-90 mm. Periodically determining the concentration of the main impurity ions in the electrolyte when the following ion concentrations in the electrolyte satisfy one of the following conditions: c (Cl-) > 0.3g/L, c (As) > 0.5g/L, c (Sb) > 0.2g/L, c (Bi) > 0.5g/L, and opening a 3-6% electrolyte in the electrolytic cell to the step 1 to prepare the cathode copper plate with the copper content of more than 99.99%.
According to the method, the acidic waste liquid is used as a leaching agent, and the low-cost leaching of the copper-containing soot is realized through two-stage leaching, so that the leaching rate is high; meanwhile, through multi-level medium circulation and solution open circuit, the auxiliary material consumption in the leaching, extraction and electrolysis processes is reduced, the impurity content in the cathode copper product is effectively reduced, and the product quality reaches the standard of A-grade copper in GB/T467-.
Example 2
The raw material components used in the examples of the present invention are shown in the following table;
copper-containing soot comprises the following main components in a unit: is based on
| Zn | Pb | Cu | Sn | Cd | Fe | Cl | As | Water content |
| 18.29 | 6.72 | 5.27 | 2.47 | 0.04 | 0.7 | 12.92 | 0.1 | 27.24 |
The spent acid is described in the following table as spent sulfuric acid as the major component, in units: g/L
| SO4 2- | Na | Mg | Ca | Al | Fe2+ |
| 385.6 | 0.52 | 0.29 | 0.14 | 0.21 | 15.3 |
Description of the drawings: the copper soot and the waste acid are used as raw materials, and the waste acid is a waste sulfuric acid solution as a main component. 1) And (3) middle leaching treatment:
taking low-leaching solution and part of copper raffinate as bottom water, firstly carrying out size mixing on the copper-containing soot and the acidic waste liquid to obtain size mixing solution, then carrying out primary leaching treatment on the size mixing solution and the bottom water for several hours, and carrying out precipitation, filtration and solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver metals; the process conditions are that the ratio of the volume L of the liquid to the weight Kg of the solid is 5-7: 1, preparing a size mixing liquid; controlling the pH of the solution to be 2.0-3.0 during the leaching treatment, adding the materials while stirring for 60-120min under the condition of continuous stirring; filtering and carrying out solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver; detecting the Cu content in the middle immersion liquid and the middle immersion slag, and controlling the Cu content in the middle immersion liquid to be 10-20 g/L; smelting the middle leaching slag by a pyrogenic process to recover lead, bismuth and silver;
2) and the second low leaching treatment is carried out,
mixing rainwater, ground washing water and recycled water after sewage treatment serving as secondary low-leaching bottom water and middle leaching residues for size mixing treatment to obtain middle leaching residue mixed solution, adding waste sulfuric acid and a low-leaching oxidant into the middle leaching residue mixed solution, performing secondary low-leaching treatment by using sodium sulfate as the low-leaching oxidant, and filtering and performing solid-liquid separation to obtain low-leaching solution and low-leaching residues; specifically, the liquid-solid ratio of secondary low-leaching bottom water to middle-leaching residue is controlled to be 3-5: 1, controlling the leaching temperature to be 50-60 ℃, and controlling the mass ratio of the low-leaching oxidant to Cu in the middle leaching residue to be 0.5-0.7; controlling the acid concentration of the solution to reach 0.3-0.6mol/L in the secondary low leaching treatment, continuously stirring for 30-60min under the condition, finally filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residue enriched with lead, bismuth and silver, and sending the obtained enriched leaching residue to the pyrogenic process again for smelting and recovering lead, bismuth and silver; returning the low-leaching solution to the bottom water leaching treatment in the step 1);
3) copper extraction treatment and copper electrolysis,
performing precision filtration on the medium immersion liquid in the step 1) to obtain precision filtration dissolving liquid, and controlling the solid content in the precision filtration dissolving liquid to be less than 0.03 g/L; adding a copper extractant to carry out Cu extraction to obtain raffinate, and recovering valuable metals Zn and As from the raffinate; washing with water, performing back extraction treatment and enrichment treatment to obtain a copper-rich solution;
deoiling the copper-rich solution after back extraction to obtain electrolyte, pumping into an electrolytic bath, electrolyzing with an anode made of lead-calcium-strontium-silver quaternary alloy and a copper plate as a cathode, and controlling the voltage and current density of the electrolytic bath to 150A/m2-200 A/m2And the same polar distance is 70mm-90mm, and a cathode copper plate with the copper content of more than 99.99 percent is prepared.
Step 3) copper extraction treatment and copper electrolysis, comprising the following steps:
A. filtering, namely performing precise filtration treatment on the primary leaching solution obtained in the step 1) to obtain a precise filtration dissolving solution; controlling the solid content in the solution of the microfiltration solution to be less than 0.03 g/L.
B. Adding a Cu extracting agent into the microfiltration dissolving solution, mixing LiX98 serving as the extracting agent with No. 260 kerosene serving as an organic phase, and controlling the content of the extracting agent: the method comprises the following steps of (1) taking No. 260 kerosene 10-25:90-75, taking a precision filtration dissolving solution as a water phase, controlling the flow ratio of the water phase to an organic phase to be 1:2-4, and carrying out Cu extraction treatment to obtain raffinate and a copper-containing organic phase; controlling Cu in the raffinate to be less than or equal to 1.0 g/L;
C. recovering the valuable metals Zn and As, namely, allowing the raffinate which is prepared in the previous step and has the mass ratio of 55-65% to enter a Zn and As valuable metal recovery process section to recover the valuable metals Zn and As, and taking the rest of the raffinate which enters the recovery process section As the middle leaching bottom water in the step 1);
D. washing with water, delivering the copper-containing organic phase to a washing section for washingThe method comprises the following steps of taking a precision filtration dissolving solution as a water phase, and controlling the concentration of a washing acid solution during washing; controlling the flow ratio of the water phase to the organic phase to be 1:40-50, feeding the water-washed organic phase obtained after water washing to a back extraction section, and obtaining a copper-rich solution after back extraction; controlling the concentration of the acid washing solution to be 0.08-0.12N, the concentration of Cu to be 25-40g/L and H+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 2.0-2.5N is used as stripping acid, and the ratio of the stripping acid to the organic phase flow containing copper is controlled to be 1:3-4, obtaining Cu concentration of 45-55g/L, H+Is a copper-rich solution of 1.5-2.0N.
E. Electrolyzing, deoiling the copper-rich solution after back extraction, pumping into an electrolytic bath, adopting a lead-calcium-strontium-silver quaternary alloy as an anode, a copper plate as a cathode, controlling the bath voltage to be 1.7V-2.1V and the current density to be 150A/m2-200 A/m2The same polar distance is 70mm-90 mm; and simultaneously periodically measuring the concentration of impurity ions in the electrolyte in the electrolytic cell, when the following ion concentrations in the electrolyte satisfy one of the following conditions: c (Cl-) is not less than 0.3g/L, c (As)
0.5g/L, c (Sb) is more than or equal to 0.2g/L, c (Bi) is more than or equal to 0.5g/L, and 3-6% of electrolyte in the electrolytic bath is used as bottom water in the step 1); preparing a cathode copper plate with the copper content of more than 99.99 percent; the cathode copper plate with the copper content of more than 99.99 percent is prepared. The method for preparing the cathode copper product can effectively reduce the impurity content in the cathode copper product, and the product quality reaches the standard of A-grade copper in GB/T467-.
The comparative example also starts from a copper-containing soot as the main component; unit: is based on
| Zn | Pb | Cu | Sn | Cd | Fe | Cl | As | Water content |
| 18.29 | 6.72 | 5.27 | 2.47 | 0.04 | 0.7 | 12.92 | 0.1 | 27.24 |
The acid leaching is performed by using sulfuric acid as a raw material. The water washing and the bottom water are both carried out by using tap water as raw materials, the concrete steps are carried out according to the prior art method, meanwhile, the sodium chlorate of the invention is not used as a leaching agent, but the raw material of the prior art such as FeCl3-HCl is used as the leaching agent, the leaching residue generated in the leaching process has more copper and zinc entrainment, and the leaching rate of the comprehensive rate of the copper and the zinc is 97.5 percent and 98.6 percent. Compared with the method, the method is not superior, and the cost of raw materials is correspondingly higher.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents. Are within the scope of the patent protection.
Claims (9)
1. A method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid, which take the copper-containing soot and the acidic waste liquid as leaching raw materials, comprises the following steps:
1) and (3) middle leaching treatment:
taking low-leaching solution and part of copper raffinate as bottom water, firstly carrying out size mixing on the copper-containing soot and the acidic waste liquid to obtain size mixing liquid, then carrying out primary leaching treatment on the size mixing liquid and the bottom water for several hours, and carrying out precipitation, filtration and solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver metals;
2) and the second low leaching treatment is carried out,
mixing rainwater, ground washing water and recycled water after sewage treatment serving as secondary low-leaching bottom water and middle leaching residues for size mixing treatment to obtain middle leaching residue mixed solution, adding waste sulfuric acid and a low-leaching oxidant into the middle leaching residue mixed solution for secondary low leaching treatment, and filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residues;
3) copper extraction treatment and copper electrolysis,
finely filtering the intermediate leaching solution obtained in the step 1) to obtain a finely filtered solution, adding a copper extractant to carry out Cu extraction to obtain raffinate,
recovering Zn and As valuable metals from raffinate; washing with water, performing back extraction treatment and enrichment treatment to obtain a copper-rich solution;
deoiling the copper-rich solution after back extraction to obtain electrolyte, pumping into an electrolytic bath, electrolyzing with an anode made of lead-calcium-strontium-silver quaternary alloy and a copper plate as a cathode, and controlling the voltage and current density of the electrolytic bath to 150A/m2-200 A/m2And the same polar distance is 70mm-90mm, and a cathode copper plate with the copper content of more than 99.99 percent is prepared.
2. The method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid as claimed in claim 1, wherein the leaching treatment in step 1) is carried out under the process conditions that the liquid-solid ratio of the acidic waste liquid to the copper soot is controlled, and the ratio of the liquid volume L to the solid weight Kg is 5-7: 1, preparing a size mixing liquid; controlling the pH of the solution to be 2.0-3.0 during the middle leaching treatment, and adding the materials while stirring for 60-120min under the condition of continuous stirring; filtering and carrying out solid-liquid separation to obtain neutral leaching solution containing copper, zinc and cadmium and neutral leaching residue containing lead, bismuth and silver; detecting the Cu content in the middle immersion liquid and the middle immersion slag, and controlling the Cu content in the middle immersion liquid to be 10-20 g/L; and (4) smelting the middle leaching slag by a pyrogenic process to recover lead, bismuth and silver.
3. The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid as claimed in claim 1, wherein the secondary low leaching treatment in step 2) is carried out by controlling the liquid-solid ratio of secondary low leaching bottom water to middle leaching residue to be 3-5: 1, controlling the secondary low leaching temperature to be 50-60 ℃, and controlling the mass ratio of the low leaching oxidant to Cu in the middle leaching residue to be 0.5-0.7; controlling the acid concentration of the solution to reach 0.3-0.6mol/L in the secondary low leaching treatment, continuously stirring for 30-60min under the condition, finally filtering and carrying out solid-liquid separation to obtain low leaching solution and low leaching residue enriched with lead, bismuth and silver, and sending the obtained enriched leaching residue to a pyrogenic process again for smelting and recovering lead, bismuth and silver; the low-leaching solution is returned to the step 1) for leaching the treated bottom water.
4. The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid as claimed in claim 1, wherein the copper extraction treatment and the copper electrolysis in the step 3) comprise the following steps:
A. filtering, namely performing precise filtration treatment on the intermediate leaching solution in the step 1) to obtain a precise filtration dissolving solution;
B. adding a Cu extracting agent into the precision filtration dissolving solution, and carrying out Cu extraction treatment to obtain raffinate and a copper-containing organic phase; controlling Cu in the raffinate to be less than or equal to 1.0 g/L;
C. recovering valuable metals Zn and As, namely, allowing raffinate with the mass ratio of 55-65% obtained in the previous step to enter a Zn and As valuable metal recovery process section to recover the valuable metals Zn and As, and taking the rest to enter the recovery process section As middle immersion bottom water in the step 1);
D. washing, namely sending the copper-containing organic phase to a washing section for washing, taking a precision filtration dissolving solution as a water phase, and controlling the concentration of a washing acid solution during washing; controlling the flow ratio of the water phase to the organic phase to be 1:40-50, feeding the water-washed organic phase obtained after water washing to a back extraction section, and obtaining a copper-rich solution after back extraction;
E. and (3) electrolyzing, namely deoiling the copper-rich solution subjected to back extraction, pumping the copper-rich solution into an electrolytic bath, and preparing a cathode copper plate with the copper content of more than 99.99% by using a lead-calcium-strontium-silver quaternary alloy as an anode and a copper plate as a cathode.
5. The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid as claimed in claim 1 or 3, wherein the low-leaching oxidant is sodium chlorate or sodium sulfate.
6. The method for preparing high-purity cathode copper by using the copper-containing soot and the acidic waste liquid as claimed in claim 1 or 4, wherein the solid content in the solution obtained by microfiltration is controlled to be less than 0.03 g/L.
7. The method for preparing high-purity cathode copper by using copper-containing soot and acidic waste liquid as claimed in claim 4, wherein in the Cu extraction in step B, M5640 or LiX98 is used as an extracting agent, and is mixed with No. 260 kerosene to be used as an organic phase, and the extracting agent is controlled to have a weight ratio of: 260# kerosene =10-25:90-75, using a microfiltration dissolving solution as a water phase, controlling the flow ratio of the water phase to an organic phase to be 1:2-4, and carrying out Cu extraction.
8. The method for preparing high purity cathode copper using copper-containing soot and acidic waste liquid as claimed in claim 4, wherein the washing in step D is performed by controlling the concentration of the washing acid solution to 0.08-0.12N, the Cu concentration to 25-40g/L and H+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 2.0-2.5N is used as stripping acid, and the ratio of the stripping acid to the organic phase flow containing copper is controlled to be 1:3-4, obtaining Cu concentration of 45-55g/L, H+Is a copper-rich solution of 1.5-2.0N.
9. The method for preparing high purity cathode copper using copper-containing soot and acidic waste liquid as claimed in claim 4, wherein the electrolysis of step E is carried out under a cell voltage of 1.7V to 2.1V and a current density ofDegree 150A/m2-200 A/m2(ii) a And simultaneously periodically measuring the concentration of impurity ions in the electrolyte in the electrolytic cell, when the following ion concentrations in the electrolyte satisfy one of the following conditions: c (Cl-) > 0.3g/L, c (As) > 0.5g/L, c (Sb) > 0.2g/L, c (Bi) > 0.5g/L, and 3-6% of electrolyte in the electrolytic bath is used As the bottom water in the step 1); the cathode copper plate with the copper content of more than 99.99 percent is prepared.
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