CN110819810A - Comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt - Google Patents
Comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 57
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 41
- 239000011701 zinc Substances 0.000 title claims abstract description 41
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- 239000010941 cobalt Substances 0.000 claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 9
- AQAJDYDFOKOJNI-UHFFFAOYSA-N [Pb].[Cu].[Co] Chemical compound [Pb].[Cu].[Co] AQAJDYDFOKOJNI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 239000003245 coal Substances 0.000 claims abstract description 5
- 238000004939 coking Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 12
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 9
- 229940000489 arsenate Drugs 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 150000002739 metals Chemical class 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000002386 leaching Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- CVXNLQMWLGJQMZ-UHFFFAOYSA-N arsenic zinc Chemical compound [Zn].[As] CVXNLQMWLGJQMZ-UHFFFAOYSA-N 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- OXSWKJLAKXNIFG-UHFFFAOYSA-N azane sulfuric acid Chemical compound N.N.N.OS(O)(=O)=O OXSWKJLAKXNIFG-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
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/04—Obtaining zinc by distilling
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
-
- 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
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- Metallurgy (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a comprehensive recovery method of zinc hydrometallurgy arsenium salt purified cobalt nickel slag, which comprises the steps of drying the zinc hydrometallurgy arsenium salt purified cobalt nickel slag in an inert atmosphere, mixing the dried cobalt nickel slag with coking coal, adding the mixture into a vacuum reduction furnace, and carrying out sectional evaporation to obtain arsenic metal powder and alloy zinc powder, wherein the furnace bottom is made of copper-cobalt-lead alloy; casting a copper-cobalt-lead alloy anode into copper sulfate electrolyte for copper electrodeposition, and performing open-circuit treatment on the electrolyte when the cobalt content reaches 5 g/L; adding the cobalt-containing electrolyte subjected to open circuit treatment into calcium hypochlorite to obtain a cobalt raw material, and returning the purified liquid subjected to cobalt precipitation to copper electrodeposition for use as the electrolyte. The recovery of the cobalt-nickel slag has the advantages of reasonable process, low separation cost, no pollution, no toxicity and the like.
Description
Technical Field
The invention relates to the field of resource utilization of cobalt-nickel slag purified by zinc hydrometallurgy arsenate, in particular to a comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenate.
Background
In the wet zinc smelting process at home and abroad, because the purification (arsenic salt purification for short) by using zinc powder and arsenic trioxide to remove cobalt has the advantages of low zinc powder consumption, good deep purification effect, high enrichment ratio of valuable metals of produced copper slag and cobalt-nickel slag and the like, the zinc sulfate solution purification of the Limited corporation of Katsukusan smelting group adopts arsenic salt to remove cobalt in a deep purification way, and the annual cobalt-nickel slag contains 42-53 percent of valuable metals, 1.5-5.0 percent of Co, 8-13 percent of Zn and 8-15 percent of As.
The cobalt-nickel slag has high content of valuable metals such as copper, cobalt and zinc, and has high recovery value, arsenic, copper, cobalt, nickel and the like in the slag exist in an alloy form, the stability is high, the components are complex, the treatment difficulty is relatively high, and the copper in the cobalt-nickel slag is recovered after some factories do not treat or simply treat the slag, so that the resource waste is caused, and the environmental pollution is easily caused; if the raw copper is sent to a copper blast furnace to recover copper, valuable metals such As zinc, cobalt and the like are not recovered, and As enters smoke or a small part of As enters crude copper or slag, so that smoke dust is difficult to recover, the As contained in the crude copper also affects electrolysis, and meanwhile, the zinc, the cobalt, the arsenic and the like entering the slag increase the slag amount, the copper smelting energy consumption increases, and the unit production cost increases.
A process for treating the purified slag for removing cobalt from antimonate in No. 9 of resource regeneration 2010 comprises the following steps: valuable metals such as zinc, cadmium, cobalt and the like are leached in an acid manner and enter a solution, copper is controlled to enter a slag leaching solution for oxidation and iron removal, zinc powder is used for copper removal, then cobalt is precipitated, and cobalt precipitation slag is subjected to acid washing and impurity removal and then is roasted to obtain cobaltosic oxide. The disadvantage of this process is that the nickel and zinc in the slag are not fully recovered. The 32 nd No. 4 of the university newspaper of Zhongnan, 2001, proposes a process for treating wet-process zinc smelting antimonate purified cobalt slag by an ammonia-ammonium sulfate system. The method can directly extract cobalt or cobalt salt and prepare active zinc powder at the same time, but the process adopts ammonium-ammonia water solution as a leaching agent, and the operation environment is relatively severe. The combined extraction process of valuable elements in cobalt-nickel slag produced by the arsenic salt purification process by pyrogenic process and wet process is reported in Chinese literature of the research and literature collection of the specialized research and discussion of the localization of zinc pressure leaching process and equipment and direct reduction of liquid lead slag. The second-stage slag is selectively zinc-dipped and the zinc-dipped slag is roasted to open the arsenic and convert the valuable metals such as copper, cobalt, nickel and the like into oxides which are easy to be leached by acid. After acid leaching of the roasting slag, removing copper by iron powder replacement to separate copper from cobalt and nickel. The process obviously has the problem of overhigh iron content in the solution after copper removal.
CN 102534235A discloses a method for recovering valuable metals from cobalt-nickel slag purified by zinc and arsenic salt hydrometallurgy, which comprises the following steps: selective leaching of sulfuric acid, calcination, secondary leaching of sulfuric acid, arsenic copper precipitation and cobalt nickel precipitation, so that valuable metals such as zinc, copper, cobalt and nickel in cobalt nickel slag can be separated and recovered. CN 102965499B discloses a method for extracting valuable elements from arsenic salt purification slag in zinc hydrometallurgy. The method adopts a full-wet process to treat the arsenic salt purification slag of the zinc hydrometallurgy, and recovers cobalt and nickel by selective zinc leaching, oxidation leaching of lead, neutralization arsenic and copper precipitation and precipitation; and (4) carrying out alkaline leaching on the arsenic-precipitated copper slag obtained by neutralizing and precipitating arsenic to separate copper and arsenic. CN 105567999B discloses a method for recovering valuable metals from cobalt-nickel slag purified by zinc and arsenic salt hydrometallurgy, which comprises the following steps: leaching zinc electrolysis waste liquid, roasting, secondary acid leaching of the zinc electrolysis waste liquid, and oxidizing and precipitating cobalt by potassium permanganate, thereby realizing the recovery of valuable metals such as Zn, Co, Ni and the like. These three methods are similar, and all have the problem of waste water discharge, and generate poisonous gas arsenic hydride in the selective zinc dipping step.
Therefore, how to find a method for effectively separating valuable metals from cobalt-nickel slag and respectively recovering the valuable metals is a problem to be further explored.
Disclosure of Invention
The invention aims to provide a comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt, aiming at the defects of the prior art, the method is environment-friendly, pollution-free, simple and feasible, the properties of valuable metals of arsenic, zinc, copper and cobalt in the cobalt-nickel slag are utilized to the maximum extent, arsenic is recovered in the form of metallic arsenic, and the recovery rate exceeds 94 percent; the zinc is recovered by alloy zinc powder, and the recovery rate exceeds 92 percent; copper is recovered by electrodeposition, and the recovery rate of copper reaches 98 percent; the cobalt is separated and recovered in the form of cobaltosic oxide, the recovery rate is over 90 percent, the process is simple, three wastes are not generated, and the method belongs to green and environment-friendly smelting.
The technical scheme of the invention is as follows:
a comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt is characterized by comprising the following steps:
step A, drying: drying the cobalt-nickel slag (hereinafter referred to as cobalt-nickel slag) purified by the zinc-arsenic salt hydrometallurgy under the protection of inert gas, wherein the drying temperature is 300-.
Step B, vacuum reduction and evaporation: b, mixing the dried cobalt-nickel slag obtained in the step A with coking coal accounting for 3-7% of the total weight percent, adding the mixture into a vacuum reduction furnace, wherein the system pressure is 20-30Pa, the temperature is 500-700 ℃, and the time is 60-90min, so as to obtain arsenic metal powder; then under the condition of unchanged pressure, the temperature is raised to 860 ℃ and 960 ℃, the time is 60-90min, zinc powder is collected, and the bottom of the furnace is made of copper-cobalt-lead alloy.
Step C, copper electrodeposition: and C, casting the copper-cobalt-lead alloy obtained in the step B into an anode, putting the anode into copper sulfate electrolyte for copper electrodeposition, wherein the control amounts of Cu and Co in the solution are 26-35g/L and 0.5-5g/L respectively, and performing open-circuit treatment on the electrolyte when the cobalt content reaches 5 g/L.
Step D, oxidizing and precipitating cobalt: and C, adding the cobalt-containing electrolyte obtained in the step C after the open circuit treatment into calcium hypochlorite which is 1.1-1.3 times of the theoretical amount of the divalent cobalt oxidized into the trivalent cobalt, adjusting the pH value to 2.5-3.5 to obtain a cobalt raw material, and returning the purified solution after cobalt precipitation to copper electrodeposition for use as the electrolyte.
As a further improvement of the invention, in the step A, the pressure is micro-positive pressure, the pressure is 30-80Pa, and the oxygen concentration is 1.5-2.8%; the inert gas refers to argon, nitrogen, carbon dioxide and other gases.
As a further improvement of the invention, in the step B, the collected zinc powder has the granularity of 200-280 meshes, and the lead content and the arsenic content are respectively 0.02-0.15 percent and 0.01-0.06 percent, and is used as arsenic salt purified zinc powder; instead of the reduced matter coking coal in this step, a reduced matter such as CO may be used.
As a further improvement of the invention, in the step C, the electrolyte is copper sulfate solution, the electrolysis temperature is 50-65 ℃, and the current density in the electrodeposition process is 130-240A/m2The addition amount of the additive gelatin is 900-.
As a further improvement of the invention, gelatin is added into the electrolyte, and the addition amount of the gelatin is 900-1400g/t & Cu.
As a further improvement of the invention, in the step D, the purification temperature is 65-75 ℃ and the time is 90-120 min.
As a further improvement of the invention, in the step D, the addition amount of the calcium hypochlorite is 1.1-1.3 times of the theoretical mass for oxidizing the divalent cobalt into the trivalent cobalt.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the cobalt-nickel slag is dried under the anoxic condition, so that metals such As Cu, Zn, Co, As and the like are prevented from being oxidized in the process, and the consumption of subsequent coking coal is reduced. Evaporating under vacuum state under two stages of different conditions, and respectively recovering to obtain metal arsenic and zinc powder; the granularity of the zinc powder obtained by the two-stage evaporation is 200-280 meshes, and the zinc powder contains a small amount of alloy, so that the zinc powder has an activating effect on the purification of the zinc powder and is more beneficial to the purification of arsenic salt; the copper-cobalt-lead alloy obtained after evaporation is different in electrochemical performance, lead forms anode mud in the form of lead sulfate for recovery, copper is separated out at a cathode, and cobalt remains in waste electrolyte and is precipitated in the form of cobaltosic oxide for recovery. Wherein the recovery rates of arsenic, copper, zinc, cobalt and lead are respectively 94%, 98%, 92%, 90% and 98.5%. The method provided by the invention can separate and recover valuable metals arsenic, copper, zinc, cobalt and lead in the cobalt-nickel slag respectively, and has the advantages of simple process and low production cost. The method provided by the invention eliminates the pollution influence of cobalt-nickel slag accumulation on the environment or the risk of arsenic metal pollutants caused by copper blast furnace treatment in the prior art, and realizes resource utilization of cobalt-nickel slag.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It is to be understood that the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention, and the present invention encompasses other embodiments and modifications thereof within the scope of the technical spirit thereof.
The embodiment of the invention provides a comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenate, and please refer to fig. 1.
The invention is further illustrated by the following specific examples.
Example 1
Step A, drying: drying the zinc hydrometallurgy arsenate purified cobalt nickel slag under the protection of nitrogen, wherein the drying temperature is 300 ℃, the drying time is 9 hours, the pressure is 30Pa, the oxygen concentration is 1.5%, and the water content of the dried material is 0.5% by mass.
Step B, vacuum reduction and evaporation: mixing the dried cobalt-nickel slag and coking coal accounting for 3 percent of the total weight, adding the mixture into a vacuum reduction furnace, wherein the system pressure is 30Pa, the temperature is 500 ℃, and the time is 90min, so as to obtain arsenic metal powder; then under the condition of unchanged pressure, the temperature is raised to 960 ℃ for 60min, zinc powder is collected, and the bottom of the furnace is made of copper-cobalt-lead alloy.
Step C, copper electrodeposition: casting copper-cobalt-lead alloy into anode, putting it into copper sulfate electrolyte for copper electrolysisThe electrolysis temperature is 50 ℃, and the current density in the electrodeposition process is 130A/m2Adding gelatin as an additive into the electrolyte, wherein the adding amount of the gelatin is 900g/t & Cu, the control amount of Cu in the solution is 26g/L, precipitating copper, and performing open-circuit treatment on the electrolyte when the cobalt content reaches 5 g/L.
Step D, oxidizing and precipitating cobalt: adding the cobalt-containing electrolyte subjected to open circuit treatment into calcium hypochlorite with the theoretical amount of 1.1 times, purifying at 65 ℃ for 120min, adjusting the pH to 3.5 to obtain a cobalt raw material, and returning the purified liquid after cobalt precipitation to copper electrodeposition for use as the electrolyte.
The method comprises the steps of comprehensively recovering cobalt-nickel slag to respectively obtain metal arsenic powder, separated copper, alloy zinc powder, cobalt raw materials and anode mud-lead slag, wherein the recovery rates of the arsenic, the copper, the zinc, the cobalt and the lead are respectively 95%, 98.1%, 93%, 90.5% and 98.6%.
Example 2
Step A, drying: and (3) drying the zinc hydrometallurgy arsenate purified cobalt-nickel slag under the protection of argon, wherein the drying temperature is 600 ℃, the drying time is 2 hours, the pressure is 80Pa, the oxygen concentration is 2.8%, and the water content of the dried material is 3.0% by mass.
Step B, vacuum reduction and evaporation: mixing the dried cobalt-nickel slag and 7 wt% of coking coal, and adding into a vacuum reduction furnace at a system pressure of 20Pa and a temperature of 700 ℃ for 60min to obtain arsenic metal powder; and then under the condition of unchanged pressure, the temperature is increased to 860 ℃ for 90min, zinc powder is collected, and the bottom of the furnace is made of copper-cobalt-lead alloy.
Step C, copper electrodeposition: casting copper-cobalt-lead alloy into anode, placing the anode into copper sulfate electrolyte to carry out copper electrodeposition, wherein the cathode is a titanium plate, the electrolysis temperature is 65 ℃, and the current density in the electrodeposition process is 240A/m2Adding 1400g/t & Cu of gelatin as additive, controlling 35g/L of Cu in solution to obtain separated copper, and performing open-circuit treatment on the electrolyte when the cobalt content reaches 5 g/L.
Step D, oxidizing and precipitating cobalt: adding the cobalt-containing electrolyte subjected to open circuit treatment into calcium hypochlorite with the theoretical amount of 1.3 times, purifying at 75 ℃ for 90min, adjusting the pH to 2.5 to obtain a cobalt raw material, and returning the purified liquid after cobalt precipitation to copper electrodeposition for use as the electrolyte.
By comprehensively recovering the cobalt-nickel slag, metal arsenic powder, separated copper, alloy zinc powder, cobalt raw materials and anode mud lead slag are respectively obtained, and the recovery rates of the arsenic, the copper, the zinc, the cobalt and the lead are respectively 94.5%, 98.3%, 94%, 90.8% and 98.7%.
Example 3
Step A, drying: drying the zinc hydrometallurgy arsenate purified cobalt nickel slag under the protection of carbon dioxide, wherein the drying temperature is 500 ℃, the drying time is 5 hours, the pressure is 50Pa, the oxygen concentration is 2.5%, and the water content of the dried material is 1.5% by mass.
Step B, vacuum reduction and evaporation: mixing the dried cobalt-nickel slag and coking coal accounting for 5 percent of the total weight, adding the mixture into a vacuum reduction furnace, wherein the system pressure is 25Pa, the temperature is 600 ℃, and the time is 80min, so as to obtain arsenic metal powder; and then under the condition of unchanged pressure, the temperature is increased to 900 ℃ for 80min, zinc powder is collected, and the bottom of the furnace is made of copper-cobalt-lead alloy.
Step C, copper electrodeposition: casting copper-cobalt-lead alloy into anode, placing the anode into copper sulfate electrolyte to carry out copper electrodeposition, wherein the electrolysis temperature is 60 ℃, and the current density in the electrodeposition process is 200A/m2The addition amount of gelatin as an additive is 1100g/t & Cu, the control amount of Cu in the solution is 30g/L, the separated copper is obtained, and the open circuit treatment is carried out on the electrolyte when the cobalt content reaches 5 g/L.
Step D, oxidizing and precipitating cobalt: adding the cobalt-containing electrolyte subjected to open circuit treatment into calcium hypochlorite with the theoretical amount of 1.2 times, purifying at 70 ℃ for 100min, adjusting the pH to 3.0 to obtain a cobalt raw material, and returning the purified liquid after cobalt precipitation to copper electrodeposition for use as the electrolyte.
The method comprises the steps of comprehensively recovering cobalt-nickel slag to respectively obtain metal arsenic powder, separated copper, alloy zinc powder, cobalt raw materials and anode mud-lead slag, wherein the recovery rates of the arsenic, the copper, the zinc, the cobalt and the lead are respectively 95.3%, 98.2%, 92.3%, 90.2% and 98.7%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt is characterized by comprising the following steps:
A. and (3) drying: drying the cobalt-nickel slag under the protection of inert gas, wherein the drying temperature is 300-;
B. vacuum reduction and evaporation: b, mixing the dried cobalt-nickel slag obtained in the step A with coking coal accounting for 3-7% of the total weight percent, adding the mixture into a vacuum reduction furnace, wherein the system pressure is 20-30Pa, the temperature is 500-700 ℃, and the time is 60-90min, so as to obtain arsenic metal powder; then under the condition of unchanged pressure, the temperature is increased to 860-960 ℃, the time is 60-90min, zinc powder is collected, and the bottom of the furnace is made of copper-cobalt-lead alloy;
C. copper electrodeposition: b, casting the copper-cobalt-lead alloy obtained in the step B into an anode, putting the anode into copper sulfate electrolyte for copper electrodeposition, wherein the control amounts of Cu and Co in the solution are 26-35g/L and 0.5-5g/L respectively, and performing open-circuit treatment on the electrolyte when the cobalt content reaches 5 g/L;
D. and (3) oxidizing and precipitating cobalt: and C, adding calcium hypochlorite into the cobalt-containing electrolyte subjected to open circuit treatment obtained in the step C, adjusting the pH to 2.5-3.5 to obtain a cobalt raw material, and returning the purified liquid after cobalt precipitation to copper electrodeposition for use as the electrolyte.
2. The comprehensive recovery method of zinc hydrometallurgy arsenate purified cobalt nickel slag according to claim 1, characterized in that: in the step A, the pressure is 30-80Pa, and the oxygen concentration is 1.5-2.8%; the inert gas refers to argon, nitrogen or carbon dioxide gas.
3. The comprehensive recovery method of zinc hydrometallurgy arsenate purified cobalt nickel slag according to claim 1, characterized in that: in the step B, the collected zinc powder has the granularity of 200-280 meshes, the lead content of 0.02-0.15 percent and the arsenic content of 0.01-0.06 percent and is used as arsenic salt purified zinc powder.
4. The synthesis of claim 1, wherein the cobalt-nickel slag is purified by arsenic salt produced in zinc hydrometallurgyThe recovery method is characterized in that: in the step C, the electrolyte is copper sulfate solution, the electrolysis temperature is 50-65 ℃, and the current density in the electrodeposition process is 130-240A/m2。
5. The comprehensive recovery method of zinc hydrometallurgy arsenate purified cobalt nickel slag according to claim 4, characterized in that: adding gelatin into the electrolyte, wherein the adding amount of the gelatin is 900-1400g/t & Cu.
6. The comprehensive recovery method of zinc hydrometallurgy arsenate purified cobalt nickel slag according to claim 1, characterized in that: in the step D, the purification temperature is 65-75 ℃ and the time is 90-120 min.
7. The comprehensive recovery method of zinc hydrometallurgy arsenate purified cobalt nickel slag according to claim 1, characterized in that: in the step D, the addition amount of the calcium hypochlorite is 1.1 to 1.3 times of the theoretical mass for oxidizing the divalent cobalt into the trivalent cobalt.
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