CN117702188A - Method for separating noble metal by multi-metal alloy controlled potential electrolysis - Google Patents
Method for separating noble metal by multi-metal alloy controlled potential electrolysis Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 61
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims description 81
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000010953 base metal Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910001439 antimony ion Inorganic materials 0.000 claims description 12
- 229910001431 copper ion Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 16
- 239000002244 precipitate Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910001316 Ag alloy Inorganic materials 0.000 abstract 1
- 229910001245 Sb alloy Inorganic materials 0.000 abstract 1
- 239000002140 antimony alloy Substances 0.000 abstract 1
- KGHMFMDJVUVBRY-UHFFFAOYSA-N antimony copper Chemical compound [Cu].[Sb] KGHMFMDJVUVBRY-UHFFFAOYSA-N 0.000 abstract 1
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a method for separating noble metals by multi-metal alloy potential-controlled electrolysis, belonging to the technical field of hydrometallurgy. The invention provides a method for separating noble metals by multi-metal alloy controlled potential electrolysis based on electrochemical principle, which utilizes the difference of oxidation potential of each metal to realize the separation of copper, antimony, noble metal gold and silver by electrochemical reaction in an electrolytic tank, and can respectively obtain cathode precipitate, namely copper-antimony alloy, anode mud and gold-silver alloy; the whole treatment process has the advantages of high metal direct yield, low energy consumption, short flow, simple equipment and the like, and is convenient for large-scale industrial production and application.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for separating noble metals by multi-metal alloy potential-controlled electrolysis.
Background
Noble metals refer to metallic elements with greater chemical stability, such as gold, silver, and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum), and the like. It is often used in the electronics and electrical industries, such as relays, resistors, catalytic converters, etc., due to its excellent corrosion resistance, stable thermoelectric properties, excellent photosensitivity, high temperature oxidation resistance, and good catalytic properties.
In nature, gold, silver and platinum group metals are rarely extracted into natural concentrates, and are basically associated with other nonferrous metals, and in fact, almost all silver, more than one half of platinum group metals and a considerable amount of gold are incidentally recovered as by-products of nonferrous metallurgy in the process of extracting main metals. Modern industrial extraction basically takes intermediate products of metallurgical and chemical operations as raw materials, such as anode slime, smelting residues and the like.
For anode slime or residue from copper-nickel smelter, aqua regia may be used to dissolve palladium, platinum and gold in the anode slime while rhodium, ruthenium, osmium, iridium and silver remain in the residue, then the aqueous solution containing platinum and palladium is treated with ammonium chloride to form a water-insoluble ammonium-containing platinum salt, which is then purified to obtain an ammonium salt which may be reduced with thermal decomposition or organic reagents to produce pure platinum. The residue insoluble in aqua regia is eutectic with lead to dissolve noble metal in lead, and various noble metals are separated through a series of complex dissolving, replacing and precipitating processes.
The electrolysis process has the advantages of simple equipment and process, low cost, no pollution and the like, and is widely applied to hydrometallurgy. However, the anode raw material composition of the electrochemical deposition metallurgy is greatly limited due to the stable chemical nature of noble metals. If the noble metal content in the anode is high, a passivation layer is formed on the surface of the anode by the noble metal in the electrolysis process, so that further electrolysis of base metal is hindered and the cell pressure is rapidly increased, thereby leading the noble metal to be oxidized into electrolyte and deposited on the cathode, and failing to achieve the expected separation effect.
With the progress of technology and the development of society, a plurality of materials with high noble metal content appear in the human society at present, and the materials cannot be effectively treated by adopting traditional metallurgy. Such as a residue obtained by vacuum distillation of a certain smelting plant Mao Yin, which contains 1-5% of Au, 3-7% of Ag, 60-75% of Cu and 15-25% of Sb in percentage by mass, the material is not used before, so that a new treatment method is required to be found for the treatment of the material. If the precious metals in the materials can be extracted efficiently, with low energy consumption and low pollution, the enterprise benefit can be greatly improved, and the resources can be fully utilized.
Disclosure of Invention
The invention aims to provide a method for separating noble metals by multi-metal alloy potential-controlled electrolysis, which can directly extract and separate noble metals from alloys produced by Mao Yin vacuum distillation and alloys with other similar components, overcomes the problems of high energy consumption, severe operation environment, large noble metal loss and the like in the traditional high-content noble metal material extraction process, and has the advantages of low energy consumption, short flow, high recovery rate and environmental friendliness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for separating noble metals by multi-metal alloy controlled potential electrolysis, which comprises the following steps:
placing a bulk multi-metal alloy in an anode tank for controlled potential electrolysis, oxidizing base metals in the multi-metal alloy into metal ions, entering an electrolyte, depositing on a cathode plate, and allowing the noble metals to fall into the anode tank without being dissolved; stripping the base metal from the cathode to obtain a base metal alloy; obtaining anode mud containing noble metals in an anode tank;
the multi-metal alloy comprises the following components in percentage by mass: 1-5% of Au, 3-7% of Ag, 60-75% of Cu and 15-25% of Sb; the base metals include Cu and Sb; the noble metal comprises Au and Ag;
the anode potential is 0.1-0.8V and the cell pressure is 0.4-1.5V during the controlled potential electrolysis.
Preferably, the anode current density of the controlled potential electrolysis is 45-250A/m 2 。
Preferably, the temperature of the electrolyte is 20-50 ℃.
Preferably, the electrolyte comprises an electrolyte, metal ions and water; the electrolyte comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, potassium sulfate, sodium chloride and potassium chloride; the metal ions include copper ions and/or antimony ions.
Preferably, the concentration of copper ions in the electrolyte is 1-30 g/L, and the concentration of antimony ions is 1-200 g/L.
Preferably, when the electrolyte comprises sulfuric acid, the concentration of sulfuric acid in the electrolyte is 10-400 g/L; when the electrolyte comprises nitric acid, the concentration of the nitric acid in the electrolyte is 10-400 g/L; when the electrolyte comprises hydrochloric acid, the concentration of the hydrochloric acid in the electrolyte is 10-400 g/L; when the electrolyte comprises hydrofluoric acid, the concentration of the hydrofluoric acid in the electrolyte is 10-200 g/L; when the electrolyte comprises potassium sulfate, the concentration of the potassium sulfate in the electrolyte is 1-100 g/L; when the electrolyte comprises sodium chloride, the concentration of the sodium chloride in the electrolyte is 1-50 g/L; when the electrolyte comprises potassium chloride, the concentration of the potassium chloride in the electrolyte is 1-80 g/L.
Preferably, the particle size of the multi-metal alloy is 1-50 mm.
Preferably, the circulation speed of the electrolyte in the controlled potential electrolysis is 20-2000 mL/min.
Preferably, the cathode plate is made of one or more of stainless steel, titanium and copper.
Preferably, the anode groove is made of one or more of terylene, acrylic and polytetrafluoroethylene; the anode tank is a porous and permeable cuboid loading box.
The invention provides a method for separating noble metals by multi-metal alloy controlled potential electrolysis based on an electrochemical principle, which develops a novel process for extracting noble metals with low cost and low pollution by utilizing larger potential difference between noble metals and base metals aiming at novel residual materials produced by vacuum distillation of a certain smelting plant Mao Yin. The method provided by the invention not only effectively recovers the noble metals in the novel materials, but also provides a new thought for the treatment of other high-content noble metal alloys.
When the base metal element exists in the electrolyte as positive ions, the base metal ions are driven by the electric field force and reduced on the cathode, so that the cathode deposition is realized. And the noble metal in the anode forms anode mud that falls into the anode tank.
In addition, in the conventional plate electrolysis, the anode area is small (compared with the bulk state), the anode current density is high when normal current is adopted, passivation is fast generated on the anode surface (as described in the background art), and if low current density is adopted, the anode dissolution efficiency is low and the production period is long. The multi-metal alloy is in a bulk form (obtained by bead splashing), has a larger surface area, can obtain lower anode current density by adopting normal current, greatly prolongs the time of anode passivation, has enough time for the copper and antimony in the alloy to react and dissolve out, and solves the problem that the traditional electrolysis cannot achieve the expected separation effect.
The method provided by the invention is simple and convenient to operate, not only solves the problem of recovering noble metals in novel smelting byproducts, but also avoids the problems of high cost, serious pollution and the like in the traditional pyrometallurgy. Meanwhile, an effective scheme is provided for extracting noble metals by a hydrometallurgical technology, and the method is beneficial to large-scale industrial popularization and application.
Drawings
FIG. 1 is a schematic diagram of an apparatus for the controlled potential electrolytic separation of noble metals from a multi-metal alloy according to the present invention.
Detailed Description
The invention provides a method for separating noble metals by multi-metal alloy controlled potential electrolysis, which comprises the following steps:
placing a bulk multi-metal alloy in an anode tank for controlled potential electrolysis, oxidizing base metals in the multi-metal alloy into metal ions, entering an electrolyte, depositing on a cathode plate, and allowing the noble metals to fall into the anode tank without being dissolved; stripping the base metal from the cathode to obtain a base metal alloy; obtaining anode mud containing noble metals in an anode tank;
the multi-metal alloy comprises the following components in percentage by mass: 1-5% of Au, 3-7% of Ag, 60-75% of Cu and 15-25% of Sb; the base metals include Cu and Sb; the noble metal comprises Au and Ag;
the anode potential is 0.1-0.8V and the cell pressure is 0.4-1.5V during the controlled potential electrolysis.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
In the present invention, the multi-metal alloy is preferably a residue obtained by vacuum distillation of a certain smelter Mao Yin; the multi-metal alloy comprises the following components in percentage by mass: 1-5% of Au, 3-7% of Ag, 60-75% of Cu and 15-25% of Sb; preferably, it comprises 2 to 4% of Au, 4 to 6% of Ag, 65 to 70% of Cu and 17 to 23% of Sb. In the present invention, the multi-metal alloy may include other noble metals in addition to Au and Ag; other base metals besides Cu and Sb may be included. In the present invention, the particle diameter of the multi-metal alloy is preferably 1 to 50mm, more preferably 3 to 20mm.
In the invention, the multi-metal alloy is preferably obtained by crushing or bead splashing; the invention does not require special requirements for the specific implementation process of the crushing and bead splashing. When the conventional plate-shaped electrolysis is carried out, the anode area is small (compared with the scattered anode), when normal current is adopted, the anode current density is high, passivation is carried out on the surface of the anode quickly (as described in the background art), and if the low current density is adopted, the anode dissolution efficiency is low and the production period is long. The multi-metal alloy is in a bulk form (obtained by bead splashing), has a larger surface area, can obtain lower anode current density by adopting normal current, greatly prolongs the time of anode passivation, has enough time for the copper and antimony in the alloy to react and dissolve out, and solves the problem that the traditional electrolysis cannot achieve the expected separation effect.
FIG. 1 is a schematic diagram of an apparatus for the controlled potential electrolytic separation of noble metals from a multi-metal alloy according to the present invention. As shown in figure 1, the electrolytic tank is filled with electrolyte, the multi-metal alloy is arranged in the anode tank and is connected with the positive electrode of a power supply and a potential recorder, the negative plate is arranged at the negative electrode end and is connected with the negative electrode of the power supply, the reference electrode is connected with the potential recorder, and the peristaltic pump circulates the electrolyte; after the electric potential control electrolytic cell is installed, a power supply is started, and the electric potential of the anode is changed by regulating and controlling the current, so that the electric potential control electrolytic cell is realized.
In the invention, the anode groove is preferably made of one or more of terylene, acrylic and polytetrafluoroethylene; the anode cell is preferably a porous, water permeable cuboid loading box. The pore size is not particularly limited, and it is preferable that the pore size is permeable to water but impermeable to anode slime. In the invention, the multi-metal alloy in the anode groove is connected with the positive electrode of a power supply through a conductive medium; the conductive medium comprises one or more of graphite and an anode.
In the invention, the material of the cathode plate preferably comprises one or more of stainless steel, titanium and copper; the reference electrode is preferably a saturated calomel reference electrode, a mercurous sulfate reference electrode or a silver chloride reference electrode.
In the present invention, the electrolytic solution preferably includes an electrolyte, metal ions, and water; the electrolyte preferably comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, potassium sulfate, sodium chloride and potassium chloride; the metal ions preferably comprise copper ions and/or antimony ions.
In the present invention, when the electrolyte includes sulfuric acid, the concentration of sulfuric acid in the electrolyte is preferably 10 to 400g/L, more preferably 50 to 350g/L, still more preferably 100 to 300g/L; when the electrolyte includes nitric acid, the concentration of nitric acid in the electrolyte is preferably 10 to 400g/L, more preferably 50 to 350g/L, still more preferably 100 to 300g/L; when the electrolyte includes hydrochloric acid, the concentration of hydrochloric acid in the electrolyte is preferably 10 to 400g/L, more preferably 50 to 350g/L, still more preferably 100 to 300g/L; when the electrolyte includes hydrofluoric acid, the concentration of hydrofluoric acid in the electrolyte is preferably 10 to 200g/L, more preferably 50 to 150g/L, still more preferably 70 to 120g/L; when the electrolyte includes potassium sulfate, the concentration of potassium sulfate in the electrolyte is preferably 1 to 100g/L, more preferably 10 to 80g/L, still more preferably 30 to 60g/L; when the electrolyte includes sodium chloride, the concentration of sodium chloride in the electrolyte is preferably 1 to 50g/L, more preferably 10 to 40g/L, still more preferably 20 to 30g/L; when the electrolyte includes potassium chloride, the concentration of potassium chloride in the electrolyte is preferably 1 to 80g/L, more preferably 10 to 70g/L, and still more preferably 20 to 50g/L.
In the present invention, when the metal ion includes copper ion, the concentration of copper ion in the electrolytic solution is preferably 1 to 30g/L, more preferably 5 to 25g/L, still more preferably 10 to 20g/L; when the metal ions include antimony ions, the concentration of antimony ions in the electrolyte is preferably 1 to 200g/L, more preferably 50 to 150g/L, still more preferably 80 to 120g/L.
In the present invention, the temperature of the electrolyte is preferably 20 to 50 ℃, more preferably 25 to 45 ℃, and even more preferably 30 to 40 ℃. In the present invention, the circulation rate of the electrolyte at the time of the controlled potential electrolysis is preferably 20 to 2000mL/min, more preferably 100 to 1800mL/min, and still more preferably 500 to 1500mL/min.
In the present invention, the anode current density of the controlled potential electrolysis is preferably 45 to 250A/m 2 More preferably 70 to 230A/m 2 More preferably 80 to 180A/m 2 。
In the invention, the anode potential is 0.1-0.8V, preferably 0.3-0.75V when the controlled potential is electrolyzed; the groove pressure is 0.4 to 1.5V, preferably 0.6 to 1.3V, more preferably 0.8 to 1V.
According to the invention, by controlling the anode potential, base metals in the multi-metal alloy are oxidized into metal ions, enter the electrolyte, deposit on the cathode plate, and the noble metals are insoluble and fall into the anode tank.
In the present invention, the base metal includes Cu and Sb; the noble metal includes Au and Ag.
Stripping base metal from a cathode to obtain base metal alloy; anode mud containing noble metal is obtained in the anode tank.
After the controlled potential electrolysis is finished, the anode slime is preferably subjected to ultrasonic vibration cleaning on the anode slime attached to the anode slime, and the obtained cleaning liquid is subjected to solid-liquid separation to obtain the anode slime containing noble metals.
The invention provides a method for separating noble metals by multi-metal alloy controlled potential electrolysis based on an electrochemical principle, which aims at a novel material produced by a certain smelting plant and develops a novel process for extracting noble metals with low cost and low pollution by utilizing a larger potential difference between noble metals and base metals. The method provided by the invention not only effectively recovers the noble metals in the novel materials, but also provides a new thought for the treatment of other high-content noble metal alloys.
The method for the controlled potential electrolytic separation of noble metals from multi-metal alloys provided by the present invention will be described in detail with reference to the examples, but they should not be construed as limiting the scope of the invention.
Example 1
Taking a proper amount of antimonous oxide to react with hydrofluoric acid, adding a certain amount of copper sulfate and sulfuric acid after clarification, finally fixing the volume to 300mL, measuring that the concentration of antimony ions is 0.9mol/L and the concentration of copper ions is 0.15mol/L, and pouring the prepared electrolyte into an acrylic electrolytic tank. And (3) pouring the multi-metal alloy into beads to obtain a scattered multi-metal alloy, adding 195.0750g of the scattered multi-metal alloy (Au 3.02%, ag 6.99%, cu 70.77% and Sb 20.86%) into an anode groove, inserting a conductive graphite rod into the middle, selecting a copper plate as a cathode, adopting an Ag/AgCl electrode as a reference electrode, and controlling the temperature of an electrolyte to be 25 ℃.
The following experiments were performed according to the conditions described above:
the anode potential was controlled to 0.75V, the cell voltage was 1.1V, and the anode current density was estimated to be 53.34A/m 2 The cathode reduction current density is 225A/m 2 And electrifying for 48 hours, respectively taking out anode mud, anode and cathode, cleaning and drying. In the deposition process, firstly, red Cu is separated out on the cathode, and Sb is gradually deposited along with the progress of the electrolysis process. The specific reaction formula is as follows:
Cu 2+ +2e - ＝Cu
Sb 3+ +3e ﹣ ＝Sb。
the resulting product was weighed and analyzed as follows:
TABLE 1 EXAMPLE 1 anode slime composition analysis results
| Anode mud component | Au | Ag | Cu | Sb |
| Content/wt% | 26.56 | 60.98 | 9.66 | 5.41 |
TABLE 2 example 1 analysis results of cathode precipitate components
| Cathode precipitate component | Au | Ag | Cu | Sb |
| Content/wt% | 0 | 0 | 76.82 | 23.68 |
The anode slime rate is 11.25%, the noble metal recovery rate is 94.45%, and the noble metal recovery rate is 98.45%.
Example 2
Taking a proper amount of antimonous oxide to react with hydrofluoric acid, adding a certain amount of copper sulfate pentahydrate and sulfuric acid after clarification, finally fixing the volume to 300mL, measuring that the concentration of antimony ions is 0.9mol/L and the concentration of copper ions is 0.15mol/L, and pouring the prepared electrolyte into an acrylic electrolytic tank. And (3) pouring the multi-metal alloy into beads to obtain a scattered multi-metal alloy, adding 273.6864g of the scattered multi-metal alloy (Au 3.19%, ag 6.95%, cu 71.59% and Sb 20.36%) into an anode groove, inserting a conductive graphite sheet in the middle, selecting a red copper plate as a cathode, adopting an Ag/AgCl electrode as a reference electrode, and controlling the temperature of an electrolyte to be 25 ℃.
The following experiments were performed according to the conditions described above:
the anode potential was controlled to 0.75V, the cell voltage was controlled to 1.1V,the cathode reduction current density is 225A/m 2 The anode current density was estimated to be 47.92A/m 2 And (3) electrifying for 60 hours, respectively taking out the anode, anode mud and cathode, cleaning and drying, wherein red Cu is firstly precipitated on the cathode in the deposition process, and Sb is gradually deposited along with the progress of the electrolysis process. The specific reaction formula is as follows:
Cu 2+ +2e - ＝Cu
Sb 3+ +3e ﹣ ＝Sb。
the resulting product was weighed and analyzed as follows:
TABLE 3 analysis results of anode mud composition of example 2
| Anode mud component | Au | Ag | Cu | Sb |
| Content/wt% | 28.18 | 60.41 | 8.75 | 5.22 |
TABLE 4 example 2 analysis results of cathode precipitate components
| Cathode precipitate component | Au | Ag | Cu | Sb |
| Content/wt% | 0 | 0 | 81.47 | 20.23 |
The anode slime rate is calculated to be 10.84%, the noble metal direct recovery rate is calculated to be 94.72%, and the noble metal recovery rate is calculated to be 98.61%.
Example 3
Taking a proper amount of antimonous oxide to react with hydrofluoric acid, adding a certain amount of copper sulfate pentahydrate and sulfuric acid after clarification, finally fixing the volume to 300mL, measuring that the concentration of antimony ions is 0.9mol/L and the concentration of copper ions is 0.15mol/L, and pouring the prepared electrolyte into an acrylic electrolytic tank. The multi-metal alloy is subjected to bead splashing to obtain a scattered multi-metal alloy, 100.3928g of scattered multi-metal alloy (Au2.89%, ag6.77%, cu71.36% and Sb 19.82%) is added into an anode groove, a conductive graphite sheet is inserted in the middle, a red copper plate is used as a cathode, and an Ag/AgCl electrode is used as a reference electrode. The electrolyte temperature was controlled to 25 ℃.
The following experiment was performed under the above conditions
The anode potential is controlled to be 0.75V, the tank voltage is controlled to be 1.1V, and the cathode reduction current density is controlled to be 225A/m 2 The anode current density was estimated to be 46.82A/m 2 Electrifying for 36h, respectively taking out anode, anode mud and cathode, cleaning, oven drying, and depositingIn the process, firstly, red Cu is separated out on the cathode, and Sb is gradually deposited along with the progress of the electrolysis process. The specific reaction formula is as follows:
Cu 2+ +2e - ＝Cu
Sb 3+ +3e ﹣ ＝Sb。
the resulting product was weighed and analyzed as follows:
TABLE 5 EXAMPLE 3 anode slime composition analysis results
| Anode mud component | Au | Ag | Cu | Sb |
| Content/% | 26.10 | 60.57 | 9.87 | 6.04 |
TABLE 6 example 3 analysis results of cathode precipitate components
| Cathode precipitate component | Au | Ag | Cu | Sb |
| Content/% | 0 | 0 | 78.52 | 22.28 |
The anode slime rate was calculated to be 10.41%, the precious metal recovery rate was 94.42%, and the precious metal recovery rate was 98.70%.
Comparative example 1
Taking a proper amount of antimonous oxide to react with hydrofluoric acid, adding a certain amount of copper sulfate pentahydrate and sulfuric acid after clarification, finally fixing the volume to 300mL, measuring that the concentration of antimony ions is 0.9mol/L and the concentration of copper ions is 0.15mol/L, and pouring the prepared electrolyte into an acrylic electrolytic tank. The multi-metal alloy is subjected to bead splashing to obtain a scattered multi-metal alloy, 213.4386g of scattered multi-metal alloy (Au2.92%, ag6.53%, cu72.61% and Sb 18.72%) is added into an anode groove, a conductive graphite sheet is inserted in the middle, a red copper plate is used as a cathode, an Ag/AgCl electrode is used as a reference electrode, and the temperature of electrolyte is controlled to be 25 ℃.
The following experiments were performed according to the conditions described above:
controlling the anode potential to be 0.85V, the cell voltage to be 1.22V and the cathode reduction current density to be 250A/m 2 Anode current density of 112.39A/m 2 And electrifying for 35 hours, respectively taking out the anode scrap, anode slime and cathode, cleaning and drying, wherein red Cu is firstly precipitated on the cathode in the deposition process, and Sb is gradually deposited along with the progress of the electrolysis process. The specific reaction formula is as follows:
Cu 2+ +2e - ＝Cu
Sb 3+ +3e ﹣ ＝Sb。
the resulting product was weighed and analyzed as follows:
TABLE 7 EXAMPLE 3 anode slime composition analysis results
| Anode mud component | Au | Ag | Cu | Sb |
| Content/% | 30.20 | 58.91 | 8.21 | 4.37 |
TABLE 8 example 3 analysis results of cathode precipitate components
| Cathode precipitate component | Au | Ag | Cu | Sb |
| Content/% | 0.0002 | 4.20 | 74.93 | 22.40 |
The anode slime rate was calculated to be 7.38%, the precious metal recovery rate was 69.59%, and the precious metal recovery rate was 98.32%. Comparative example 1 resulted in an excessive anode potential, leading to Ag ions entering the electrolyte and depositing on the cathode plate, and further leading to a decrease in the direct yield of noble metals.
Comparative example 2
Taking a proper amount of antimonous oxide to react with hydrofluoric acid, adding a certain amount of copper sulfate pentahydrate and sulfuric acid after clarification, finally fixing the volume to 300mL, measuring that the concentration of antimony ions is 0.9mol/L and the concentration of copper ions is 0.15mol/L, and pouring the prepared electrolyte into an acrylic electrolytic tank. Casting a multi-metal alloy into a cast plate (the rear area of the cast plate is 0.00528 m) 2 156.23 g) is connected with the positive electrode of a power supply, the cathode adopts a red copper plate, the reference electrode adopts an Ag/AgCl electrode, and the temperature of the electrolyte is controlled to be 25 ℃.
The following experiments were performed according to the conditions described above:
the initial anode potential is controlled to be 0.17V, the cell voltage is controlled to be 0.41V, and the cathode reduction current density is controlled to be 147A/m 2 At this time, the anode current density was 150A/m 2 After 5h of power on, the anode potential rises to 0.94V, the cell pressure rises to 1.39V, white turbidity appears on the electrolyte and the anode surface, and the Ag content in the electrolyte is 0.67g/L
According to experimental phenomena, the plate-shaped anode is easy to passivate during electrolysis, the stable electrolysis period is short, and silver is quickly dissolved out from the anode. Comparative example 2 has a small anode area and a large current density, which causes Ag ions to enter the electrolyte and deposit on the cathode plate, thereby causing a decrease in the direct yield of noble metals.
As can be seen from the above examples and comparative examples, the present invention provides a method for the controlled potential electrolytic separation of noble metals from multi-metal alloys, which can directly extract and separate noble metals from alloys produced by Mao Yin vacuum distillation and alloys of other similar components, overcomes the problems of high energy consumption, severe operating environment, large noble metal loss, etc. in the traditional extraction process of high-content noble metal materials, and has the advantages of low energy consumption, short flow, high recovery rate, and environmental friendliness.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for separating noble metals by multi-metal alloy controlled potential electrolysis, which is characterized by comprising the following steps:
placing a bulk multi-metal alloy in an anode tank for controlled potential electrolysis, oxidizing base metals in the multi-metal alloy into metal ions, entering an electrolyte, depositing on a cathode plate, and allowing the noble metals to fall into the anode tank without being dissolved; stripping the base metal from the cathode to obtain a base metal alloy; obtaining anode mud containing noble metals in an anode tank;
the multi-metal alloy comprises the following components in percentage by mass: 1-5% of Au, 3-7% of Ag, 60-75% of Cu and 15-25% of Sb; the base metals include Cu and Sb; the noble metal comprises Au and Ag;
the anode potential is 0.1-0.8V and the cell pressure is 0.4-1.5V during the controlled potential electrolysis.
2. The method according to claim 1, wherein the anodic current density of the potentiometric electrolysis is 45-250A/m 2 。
3. The method of claim 1, wherein the electrolyte is at a temperature of 20 to 50 ℃.
4. A method according to claim 1 or 3, wherein the electrolyte comprises an electrolyte, metal ions and water; the electrolyte comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, potassium sulfate, sodium chloride and potassium chloride; the metal ions include copper ions and/or antimony ions.
5. The method according to claim 4, wherein the concentration of copper ions in the electrolyte is 1 to 30g/L and the concentration of antimony ions is 1 to 200g/L.
6. The method of claim 4, wherein when the electrolyte comprises sulfuric acid, the concentration of sulfuric acid in the electrolyte is 10 to 400g/L; when the electrolyte comprises nitric acid, the concentration of the nitric acid in the electrolyte is 10-400 g/L; when the electrolyte comprises hydrochloric acid, the concentration of the hydrochloric acid in the electrolyte is 10-400 g/L; when the electrolyte comprises hydrofluoric acid, the concentration of the hydrofluoric acid in the electrolyte is 10-200 g/L; when the electrolyte comprises potassium sulfate, the concentration of the potassium sulfate in the electrolyte is 1-100 g/L; when the electrolyte comprises sodium chloride, the concentration of the sodium chloride in the electrolyte is 1-50 g/L; when the electrolyte comprises potassium chloride, the concentration of the potassium chloride in the electrolyte is 1-80 g/L.
7. The method of claim 1, wherein the multi-metal alloy has a particle size of 1 to 50mm.
8. The method according to any one of claims 1 to 3 and 5 to 6, wherein the circulation rate of the electrolyte at the time of the controlled potential electrolysis is 20 to 2000mL/min.
9. The method of claim 1, wherein the material of the cathode plate comprises one or more of stainless steel, titanium, and copper.
10. The method of claim 1, wherein the anode cell material comprises one or more of polyester, acrylic, and polytetrafluoroethylene; the anode tank is a porous and permeable cuboid loading box.
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