CN111118306A - Method for removing sodium and sulfur from crude antimony and enriching gold - Google Patents
Method for removing sodium and sulfur from crude antimony and enriching gold Download PDFInfo
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- CN111118306A CN111118306A CN202010044909.2A CN202010044909A CN111118306A CN 111118306 A CN111118306 A CN 111118306A CN 202010044909 A CN202010044909 A CN 202010044909A CN 111118306 A CN111118306 A CN 111118306A
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 139
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000010931 gold Substances 0.000 title claims abstract description 64
- 239000011734 sodium Substances 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 59
- 239000011593 sulfur Substances 0.000 title claims abstract description 55
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 50
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 46
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims description 20
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims 3
- 238000010612 desalination reaction Methods 0.000 claims 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000001636 atomic emission spectroscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 oxalic acid ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910052959 stibnite Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- KAPYVWKEUSXLKC-UHFFFAOYSA-N [Sb].[Au] Chemical compound [Sb].[Au] KAPYVWKEUSXLKC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BMYPOELGNTXHPU-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxastibolan-2-yl) oxalate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BMYPOELGNTXHPU-UHFFFAOYSA-H 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QUCZBHXJAUTYHE-UHFFFAOYSA-N gold Chemical compound [Au].[Au] QUCZBHXJAUTYHE-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- DGCPSAFMAXHHDM-UHFFFAOYSA-N sulfuric acid;hydrofluoride Chemical compound F.OS(O)(=O)=O DGCPSAFMAXHHDM-UHFFFAOYSA-N 0.000 description 1
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- 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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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for removing sodium and sulfur from crude antimony and enriching gold, belonging to the technical field of metallurgy; firstly, placing crude antimony in a front melting furnace of a vacuum furnace, heating to 650-700 ℃ in an inert atmosphere, and keeping the temperature for 30-180 min to convert complex crystalline salts of sodium and sulfur in the crude antimony into simple crystalline salts of sodium and sulfur, simultaneously melting antimony in the crude antimony and insolubilizing the simple crystalline salts of sodium and sulfur, and obtaining low-sodium-sulfur crude antimony after slagging off; then placing the low-sodium crude antimony in a vacuum furnace, controlling the pressure in the vacuum furnace to be 1-20 Pa through a vacuum pump, heating to 700-900 ℃, keeping the temperature for 15-60 min, volatilizing antimony in the crude antimony and condensing in a condensation zone, and enriching gold in residues; the method has the advantages of high sodium and sulfur removal efficiency, good quality of the obtained antimony metal, obvious gold enrichment effect, high direct yield, simple process flow, no pollution to the environment and the like.
Description
Technical Field
The invention relates to a method for removing sodium sulfide and enriching gold from crude antimony, belonging to the technical field of metallurgy.
Background
The antimony-gold symbiotic resource is an important component of antimony and gold resources in China, gold in the resource is tightly combined with metal sulfide, and most of the gold is embedded in stibnite, pyrite and arsenopyrite in a particulate form, so that the conventional beneficiation method is difficult to realize effective separation of antimony and gold. The sodium sulfide leaching process utilizes the characteristic that antimony sulfide is easy to react with alkali metal sulfide and gold is not reacted with alkali metal sulfide, and has wide application in the aspect of treating antimony-containing gold ores; na is commonly used industrially2S and NaOH mixed solution is used for leaching the antimony-containing gold ore to obtain antimony-containing leaching solution and gold-rich residue; the antimony-containing leachate is subjected to electrodeposition to obtain metallic antimony, and gold is extracted from the gold-rich residue by a cyanidation method, so that the separation and recovery of antimony and gold are realized. But Na in the leach solution during leaching2S is easily oxidized into Na2S2O6、Na2SXWhen complex salts of sodium and sulfur are used, gold can react with partial oxidation products to enter leaching liquid, and the gold is reduced and separated out along with antimony during electrodeposition; the electrowinning barren solution can not effectively remove Na during concentration and crystallization2Oxidation products of S, Na in leach liquor2The concentration of S oxidation products is continuously increased, partial oxidation products are easy to crystallize and separate out at a cathode during electrodeposition, so that crude antimony is obtained from antimony-containing gold ore through an alkaline leaching-electrodeposition process, sodium and sulfur are representative impurities, and a certain amount of gold is contained to be recovered.
The prior crude antimony refining methods include a reverberatory furnace refining method, an aqueous solution electrolytic refining method and a molten salt electrolytic refining method.
The reverberatory furnace refining method utilizes the characteristic that impurities in the crude antimony are easier to oxidize or vulcanize than antimony, controls proper conditions to remove the impurities by slagging, and is mainly used for refining and smelting crude antimony (containing no Na and more Sb than S) by a pyrogenic process at present2S3In the form of sodium carbonate) is usually added as a desulfurizing agent to make sulfur Na2S、Na3S3Sodium salt dross such as Sb. But the usage amount of the soda ash is large when the sulfur is removed by the reverberatory furnace refining method; the impurity removal efficiency is low, sulfur needs to be refined for many times to meet the requirement of antimony refining, and the impurity removal period is long; gold in the crude antimony cannot be enriched, and effective separation of antimony and gold is difficult to realize.
The water solution electrolytic refining process includes casting coarse antimony into anode plate, setting the anode plate and the cathode plate inside hydrofluoric acid-sulfuric acid electrolyte, electrolyzing with DC current to eliminate positive impurity and to make the impurity enter anode mud, dissolving antimony and negative impurity into the electrolyte, depositing and separating antimony on the cathode, and maintaining the negative impurity in the electrolyte to realize coarse antimony refining. The patent CN108221000A discloses 'electrolyte for electrorefining crude antimony or electrodepositing antimony' and application thereof, which is characterized in that an antimony oxalate hinge solution system is used as an electrolyte system and comprises 120-260 g/L oxalic acid ions, 25-55 g/L ammonium ions and 50-110 g/L antimony ions, silver-containing crude antimony has direct current, and the cathode current density is 100-400A/m2The distance between the cathode plate and the anode plate is 30-50 mm, and the electrolysis temperature is 25-60 ℃, and the electrolysis time is 24-72 hThe required refined antimony and noble metal silver are enriched in the anode mud. The aqueous solution electrolytic refining method can enable precious metals in crude antimony to enter anode mud to realize the enrichment of the precious metals, but the method has high requirements on an electrolyte system, sodium and sulfur in the crude antimony obtained from antimony-containing gold ores through an alkaline leaching-electrodeposition process exist in a complex crystal salt form with good water solubility, the complex crystal salt is dissolved in the electrolyte during electrodeposition to pollute the electrolyte, and meanwhile, the method also has the problems of poor electrolysis environment, large amount of electrolysis waste liquid, difficulty in treatment and the like.
The molten salt electrolytic refining is to adopt mixed molten salt with lower melting point as electrolyte, molten crude antimony as anode or cathode, insoluble metal or graphite as conductive electrode, and impurity metal is continuously migrated from the crude antimony in the high-temperature electrolysis process, thereby achieving the effect of purifying the crude antimony. The molten salt electrolytic refining method needs to be carried out at high temperature, the structure of an electrolytic cell is complex, the purification of electrolyte is more difficult compared with the waste liquid after the electrolytic refining of aqueous solution, and in addition, the electrode process dynamics is not researched yet, so the method is still in the experimental stage at present.
Crude antimony produced by a precipitation smelting method is subjected to vacuum distillation refining in 'crude antimony vacuum distillation refining' of Leshulan of Kunming institute of technology, the temperature is kept at 680-750 ℃ and the pressure is 133Pa for 10min, and refined antimony basically meeting the national standard requirement is obtained by one-time distillation, but the method cannot effectively remove impurity sulfur, the content of sulfur in obtained antimony volatile matter cannot meet the national standard requirement, and meanwhile, the sulfur in the crude antimony described in the text is Sb2S3Or FeS or simple substance S, and does not contain impurity sodium, and the removal of sodium and sulfur by the vacuum distillation process of crude antimony containing sodium and sulfur and the presence of sodium in the form of complex crystalline salt is not described.
Patent CN108411121A discloses "a method for preparing gold-silver alloy from precious antimony", which is characterized in that: firstly, melting and slagging off the precious antimony in a reverberatory furnace, adding quartz sand to remove iron, blowing ash and adding lead ash to blow to obtain antimony oxide smoke dust and precious lead; the rich and precious lead is subjected to slag removal, sulfur and sulfur addition for copper removal, oxygen introduction for sulfur removal and copper removal in a lead melting furnace; and (3) after copper removal, feeding the rich and noble lead into a vacuum furnace, and carrying out vacuum distillation at the constant temperature of 700-800 ℃ to obtain the gold-silver alloy. The method has the advantages of long flow, complex operation, large impurity and slag removal amount, sulfur removal in the form of sulfur dioxide, environmental friendliness, recovery of antimony in the form of antimony oxide, poor antimony oxide quality and low gold and silver recovery rate.
Patent CN106222424A discloses a method for comprehensively recovering precious and base metals from precious antimony alloys, which mainly comprises the steps of 'precious antimony chlorination leaching silver and base metals-gold-containing slag chlorination gold dissolving-recovery silver and base metals-lead gold slag separation lead gold-gold slag reduction and refining', and realizes the recovery of precious and base metals through multiple leaching, filtering and reduction. The method has long flow and complex operation, needs a plurality of different reducing agents, and the obtained metallic antimony does not meet the requirements of national standard on refined antimony.
Patent CN1687469A discloses a vacuum distillation purification method and a device thereof for metallic antimony, which are characterized in that the impurity removal of the metallic antimony is realized by means of one-time vacuum distillation and multi-stage condensation. Firstly, crushing 1# industrial antimony (the content of antimony is more than 99.85%) into irregular blocks with the diameter of 20-40 mm, putting the irregular blocks into an evaporator of a special vertical vacuum rectifying furnace, controlling the temperature of an evaporation area to be 700-800 ℃ and the pressure of a vacuum chamber to be 0.1-1.0 Pa, and melting metal antimony to form antimony vapor which is volatilized and ascended; the condensation zone of the vertical vacuum rectifying furnace consists of tower plates, a condenser, a collector and a collector cover plate, wherein the temperature of the condensation zone 1-3 is controlled to be 500-600 ℃, the temperature of the condensation zone 4 is controlled to be 300-400 ℃, the temperature of the collector is controlled to be 120-150 ℃, and 4N metal antimony is obtained at the condenser after constant temperature is 12-18 hours.
Disclosure of Invention
The invention provides a high-efficiency and clean method for removing sodium sulfide and enriching gold from crude antimony, aiming at the problems of the existing processes for removing sodium sulfide and enriching gold from crude antimony. The invention takes crude antimony obtained by an alkaline leaching-electrodeposition process of antimony-containing gold ore as a raw material, removes sodium and sulfur by a method of melting and slagging-off and vacuum distillation, realizes the enrichment of the gold and obtains refined antimony meeting the national standard requirements.
The method for removing sodium and sulfur from crude antimony and enriching gold comprises the following specific steps:
(1) firstly, placing crude antimony in a front melting furnace of a vacuum furnace, heating to 650-700 ℃ in an inert atmosphere, and keeping the temperature for 30-180 min to convert complex crystalline salts of sodium and sulfur in the crude antimony into simple crystalline salts of sodium and sulfur, simultaneously melting antimony in the crude antimony and insolubilizing the simple crystalline salts of sodium and sulfur, and obtaining low-sodium-sulfur crude antimony after slagging off;
(2) and (3) placing the low-sodium-sulfur crude antimony into a vacuum furnace, controlling the pressure in the vacuum furnace to be 1-20 Pa through a vacuum pump, heating to 700-900 ℃, and keeping the temperature for 15-60 min to obtain refined antimony and gold-rich residues.
The inert atmosphere is argon or nitrogen.
The crude antimony is obtained by an alkaline leaching-electrodeposition process for antimony-containing gold ores, wherein the content of Sb in the crude antimony is 80-95%, the content of Na in the crude antimony is 0.4-6.5%, the content of S in the crude antimony is 1.5-4.3%, the content of Au in the crude antimony is 40-160 g/t, the content of Fe in the crude antimony is 0.1-0.5%, the content of As in the crude antimony is 0.03-0.12%, the content of Se in the crude antimony is 0.03-0.11%, and the crude antimony further comprises impurities such As Cu, Ca, K, Zn, Si and the like, but does not contain Pb and Bi, wherein sodium and sulfur are NaS3、Na2S2O6、Na2SXAnd the like, exist as complex crystalline salts of sodium and sulfur.
The low-sodium-sulfur crude antimony contains 95-99% of Sb, 0.005-0.4% of Na, 0.005-0.3% of S and 100-300 g/t of Au.
The invention has the beneficial effects that:
(1) the sodium and sulfur in the crude antimony can be efficiently removed without adding other auxiliary additives in the refining process;
(2) the obtained refined antimony meets the national standard requirements, and gold is almost completely enriched in residues without loss;
(3) the method has the advantages of simple operation flow, almost no influence on the environment, high impurity removal efficiency and good effect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be described in more detail with reference to the following figures and embodiments, but the scope of the invention is not limited thereto.
Example 1: as shown in figure 1, the method for removing sodium and sulfur from crude antimony and enriching gold comprises the following steps:
(1) adding crude antimony (the mass percent of Sb is 83.78%, the Na content is 5.55%, the S content is 3.41%, the Au content is 150.05g/t, the Fe content is 0.25%, the As content is 0.067%, and the Se content is 0.049%) into a preposed melting furnace of a vacuum furnace, heating to 650 ℃ in an argon atmosphere, and keeping the temperature for 60min, so that complex crystalline salts of sodium and sulfur in the crude antimony are converted into simple crystalline salts of sodium and sulfur, meanwhile, antimony in the crude antimony is melted, the simple crystalline salts of sodium and sulfur are insoluble, and the low-sodium-sulfur crude antimony is obtained after slagging off (the mass percent of Sb is 97.12%, the Na content is 0.17%, the S content is 0.22%, and the Au content is 210.53 g/t);
(2) adding low-sodium crude antimony into a vacuum furnace, setting the pressure in the vacuum furnace to be 5Pa, setting the temperature in a distillation area to be 700 ℃, setting the distillation time to be 50min, obtaining refined antimony in a condensation area, and obtaining a gold-rich residue at the bottom of a crucible; the refined antimony is detected by chemical analysis and inductively coupled atomic emission spectrometry (ICP-AES) to obtain the refined antimony with the Sb content of more than 99.5 percent by mass percent and other main impurities as follows: na 0.0025%, S0.0027%, Fe 0.0022%, As 0.033%, Se 0.00010%, Cu0.00094%, Au 0.21g/t, and Au content in residue is 1947.82 g/t.
Example 2: the method for removing sodium and sulfur from crude antimony and enriching gold comprises the following steps:
(1) adding crude antimony (the mass percent content of Sb is 93.69%, the Na content is 0.4%, the S content is 1.53%, the Au content is 48g/t, the Fe content is 0.17%, the As content is 0.044%, and the Se content is 0.033%) into a preposed melting furnace of a vacuum furnace, heating to 670 ℃ in an argon atmosphere, keeping the temperature for 120min, converting complex crystalline salts of sodium and sulfur in the crude antimony into simple crystalline salts of sodium and sulfur, simultaneously melting antimony in the crude antimony and insolubilizing the simple crystalline salts of sodium and sulfur, and obtaining low-sodium-sulfur crude antimony after slagging off (the mass percent content of Sb is 98.53%, the Na content is 0.09%, the S content is 0.11%, and the Au content is 170.27 g/t);
(2) adding low-sodium crude antimony into a vacuum furnace, setting the pressure in the vacuum furnace to be 10Pa, setting the temperature in a distillation area to be 800 ℃, setting the distillation time to be 30min, obtaining refined antimony in a condensation area, and obtaining a gold-rich residue at the bottom of a crucible; the refined antimony is detected by chemical analysis and inductively coupled atomic emission spectrometry (ICP-AES) to obtain the refined antimony with the Sb content of more than 99.5 percent by mass and the specific impurity content as follows: na 0.0019%, S0.0018%, Fe 0.0017%, As 0.025%, Se 0.00009%, Cu0.00026%, Au 0.59g/t, and Au content in residue 2691.51 g/t.
Example 3: the method for removing sodium and sulfur from crude antimony and enriching gold comprises the following steps:
(1) adding crude antimony (the mass percent of Sb is 89.75%, the mass percent of Na is 3.2%, the mass percent of S is 2.19%, the mass percent of Au is 109.45g/t, the mass percent of Fe is 0.12%, the mass percent of As is 0.079%, and the mass percent of Se is 0.037%) into a preposed melting furnace of a vacuum furnace, heating to 700 ℃ in an argon atmosphere, keeping the temperature for 30min, converting complex crystalline salts of sodium and sulfur in the crude antimony into simple crystalline salts of sodium and sulfur, simultaneously melting antimony in the crude antimony and insolubilizing the simple crystalline salts of sodium and sulfur, and obtaining low-sodium-sulfur crude antimony after slagging off (the mass percent of Sb is 98.21%, the mass percent of Na is 0.11%, the mass percent of S is 0.13%, and the mass percent of Au is 220.51 g/t);
(2) adding low-sodium crude antimony into a vacuum furnace, setting the pressure in the vacuum furnace to be 15Pa, setting the temperature in a distillation area to be 900 ℃, setting the distillation time to be 20min, obtaining refined antimony in a condensation area, and obtaining a gold-rich residue at the bottom of a crucible; the refined antimony is detected by chemical analysis and inductively coupled atomic emission spectrometry (ICP-AES) to obtain the refined antimony with the Sb content of more than 99.5 percent by mass and the specific impurity content as follows: na0.0020%, S0.0019%, Fe 0.0018%, As0.026%, Se 0.00009%, Cu 0.00027%, and Au 0.61g/t, and the Au content in the residue is 2583.17 g/t.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
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