CN104746105B - It is a kind of to separate the device and method containing antimony alloy - Google Patents
It is a kind of to separate the device and method containing antimony alloy Download PDFInfo
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- CN104746105B CN104746105B CN201510172883.9A CN201510172883A CN104746105B CN 104746105 B CN104746105 B CN 104746105B CN 201510172883 A CN201510172883 A CN 201510172883A CN 104746105 B CN104746105 B CN 104746105B
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- antimony alloy
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- 229910001245 Sb alloy Inorganic materials 0.000 title claims abstract description 79
- 239000002140 antimony alloy Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 62
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 124
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 122
- 150000003839 salts Chemical class 0.000 claims abstract description 74
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 claims abstract description 53
- 239000004332 silver Substances 0.000 claims abstract description 53
- 229910052737 gold Inorganic materials 0.000 claims abstract description 42
- 239000010931 gold Substances 0.000 claims abstract description 42
- 239000002893 slag Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 239000002826 coolant Substances 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- 235000002639 sodium chloride Nutrition 0.000 claims description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004458 analytical method Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- 239000011819 refractory material Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000007770 graphite material Substances 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000009304 pastoral farming Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 16
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000011133 lead Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KAPYVWKEUSXLKC-UHFFFAOYSA-N [Sb].[Au] Chemical compound [Sb].[Au] KAPYVWKEUSXLKC-UHFFFAOYSA-N 0.000 description 2
- 238000000184 acid digestion Methods 0.000 description 2
- -1 after electrolysis Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910015363 Au—Sn Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QQHJESKHUUVSIC-UHFFFAOYSA-N antimony lead Chemical compound [Sb].[Pb] QQHJESKHUUVSIC-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process 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
- 239000010946 fine silver Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A kind of to separate the device and method containing antimony alloy, described device includes heating furnace, cathode molten pool, anode molten bath, the positive plate for being provided with perforate, cathode molten pool cover plate, return duct, loading hopper, anode stub, cathode bar and negative electrode slag outlet valve；Also include holding furnace, holding furnace cover plate, anode molten bath bearing, cathode bar coolant jacket, anode stub coolant jacket, heating furnace dodge gate and holding furnace dodge gate.Methods described includes：（1）Fusing contains antimony alloy：Fused salt dispensing, adds in molten bath by several times, heating, after fused salt melting, adds and contains antimony alloy, fusing；（2）Electrolysis fused salt：Direct current is connected, is electrolysed, discharge negative electrode slag and anode slime respectively after the completion of electrolysis.Anode slime further chlorination, displacement reduction can extract metal.Present invention process is environment-friendly, separates the rate of recovery >=99% containing antimony alloy, and gold, silver direct yield is up to 99.9% in your antimony, it is adaptable to various to be separated containing antimony alloy.
Description
Technical field
The device and method containing antimony alloy is separated the present invention relates to a kind of, and in particular to one kind is using molten-salt electrolysis from containing antimony
The foreign metals such as lead, copper, nickel or antimony are separated in alloy, gold, silver is enriched with and is reclaimed the device and method of antimony.
Background technology
It is non-ferrous metal containing antimony containing antimony alloy（Including noble metal）A kind of byproduct produced in smelting process, such as,
High lead-antimony ore deposit by the lead-antimony alloy that is obtained after smelting, your antimony obtained after being smelted containing Au-Sn deposit etc..The generation process of your antimony is：
Antimony gold concentrate, by preliminary concentration gold and silver, your antimony containing gold and silver is obtained during pyrometallurgical smelting, and further volatilization blowing is obtained
Gold and silver content rich and honour antimony higher.Vague generalization in rich and honour antimony is studied and is divided into：Gold 0.1~3.5%, silver 0.01~0.10%, antimony 30
~40%, lead 10~30%, copper 10~20%, iron 0.5~1%, nickel 0~10%, arsenic 0.5~1%.At present, the processing method of rich and honour antimony
Predominantly, hydrogen peroxide oxidation is leached and aqueous solution electrolysis mode carries gold.
The method of hydrogen peroxide oxidation leaching method enriching noble metals from noble antimonial alloy as disclosed in CN100497672C, be
By your antimony by being crushed to 60~200 mesh, potassium cloride is then carried out in the presence of hydrochloric acid, sodium chloride and hydrogen peroxide, soaked
After the completion of going out, hydrochloric acid for dreg and water washing are filtered in hot lower filtering, obtain thick gold.The method exist shortcoming be：（1）Containing lead high,
Your antimony toughness of high-copper is big, and fine grinding is extremely difficult, need to be crushed to 60~200 mesh, and difficulty is larger；（2）Iron, lead, copper in your antimony,
Nickel, antimony foreign metal are all removed, it is necessary to consume substantial amounts of hydrochloric acid and hydrogen peroxide by oxidation, chlorination, meanwhile, produce substantial amounts of
Chloride, brings substantial amounts of waste water；（3）Washing process is complicated, produces substantial amounts of sour water；（4）During reclaiming antimony, using water
Solution mode, equally produces the substantial amounts of waste water containing hydrochloric acid；（5）Process is slightly long, and reagent used is final into waste water, thus into
This height, noble metal direct yield is relatively low.
The process of aqueous solution electrolysis method is that rich and honour antimony is cast into positive plate is electrolysed, and concentration of precious metal is in antimony anode
In mud, the earth of positive pole is through nitric acid digestion removing copper, lead, nitric acid digestion slag crucible for smelting, then is waved with Muffle furnace and blow antimony, obtains thick
Gold.The method exist shortcoming be：（1）When impurity content is high in your antimony, electrolysis is difficult to down, causes gold, silver to be difficult to be enriched with；
（2）Process is more, and return slag is more, and such as crucible for smelting and Muffle furnace are waved to blow and all produce more slag, cause noble metal direct yield low；
（3）Process produces more pollutant, such as waste residue, acid-bearing wastewater and the waste gas containing nitrogen oxide etc..CN101580947A is public
A kind of method of the expensive antimony of electrolytic separation is opened, its technical scheme for using is：By xylitol, NaOH, antimony oxide, water
Mix in proportion, be configured to electrolyte, your antimony founding is positive plate, and negative electrode is stainless steel plate, and electrolyte is injected in a cell,
Place negative electrode and anode, maintain electrolyte circulation rate, be passed through direct current, metallic antimony is deposited on negative electrode, gold, silver and other are miscellaneous
Matter metal enrichment is in the earth of positive pole.The method uses solution system Inner electrolysis, in this system, by antimony and gold, silver and
Other impurities metal is separated, because aqueous conductive is weak（Fused salt electric conductivity is the 10 of the aqueous solution8Times, i.e. the conduction of the aqueous solution
Property is only the 1/10 of fused salt electric conductivity8）, thus, the current density in electrolytic process is small, and electrolytic speed is slow, when causing electrolysis
Between long, the change of the acid-base property in the aqueous solution in addition, further result in some metal impurities into sediment, it is impossible to by electrolysis
Separate, simultaneously as mechanical entrapment, causes many metals to separate, and direct yield is relatively low etc., the method separating effect is not good.
CN104313643A discloses a kind of method that two sections of fused salt electrolysis processes produce high purity antimony, and the method first uses anode process
Electrolysis removes the impurity of the standard electrode potential less than antimony, then using cathode method electrolysis, by the metal Na in electrolyte+In negative electrode
Metal is reduced to, arsenic, sulphur, bismuth is removed with impurity element chemical combination afterwards.The method is used to produce high purity antimony, it is desirable to miscellaneous in needle antimony
Matter content is low, if impurity content is too high, its efficiency can reduce many, meanwhile, electrolysis time can be longer, to obtain 99.99%
Metallic antimony, its direct yield will be extremely low, does not have use value, therefore, the method is not suitable for processing impurity content needle antimony electrolysis high.
In addition, its electrolytic cell also has the following disadvantages：One is electrolysed at 700~900 DEG C, and fused salt highly volatile is not having back
In the case of stream device, fused salt volatilization loss greatly, causes environmental degradation；Two is yin, yang electrode in electrolytic cell with one
In molten bath, the cathode and anode product inconvenience after electrolysis is separated and removed, and causes operating difficulties, or even is easy to obscure cathode and anode product
Thing.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of rational in infrastructure, are easy to operation, operation safety and environmental protection point
From the device containing antimony alloy.
The technical problem further to be solved of the invention is to overcome the shortcomings of to have contained antimony alloy processing method, there is provided one
Plant gold, silver direct yield high, technical process is simple, and accessory substance is few, the method for the separation containing antimony alloy of low cost.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of device of the separation containing antimony alloy, including
Heating furnace, cathode molten pool, anode molten bath, the positive plate for being provided with perforate, return duct, loading hopper, anode stub, cathode bar and negative electrode slag
Outlet valve；The cathode molten pool is located in heating furnace, and is coated with cathode molten pool cover plate, is accessed on the cathode molten pool cover plate cloudy
Pole rod；The anode molten bath is suspended from cathode molten pool, and anode stub passes through cathode molten pool cover plate, and anode stub end is fixed with positive plate
Connection, makes positive plate be suspended from anode molten bath；The return duct is stretched into cathode molten pool through cathode molten pool cover plate；The charging
Bucket is stretched into anode molten bath through cathode molten pool cover plate and positive plate；The cathode molten pool cover plate is provided with thermometric observation and anode
Residue discharging opening, the thermometric observation and anode slime discharging opening correspond to the perforate on positive plate；The negative electrode slag outlet valve
Positioned at cathode molten pool bottom.Apparatus of the present invention separate anode molten bath and cathode molten pool, are conducive to separating the anode and cathode after being electrolysed
Material；Cathode bar and anode stub are used for external power supply；The positive plate can be various shapes, and area is conducive to improving electrolysis energy greatly
Power, area is maximum when for disc, and electrolysis effectiveness is optimal, and perforate is additionally provided with positive plate, for feeding and discharging；Described time
Flow tube is extended down into cathode molten pool or in anode molten bath, but leaves space with fused salt, the conduct of condenser pipe is played, with true
The electrolyte cooling that guarantor is evaporated is returned in cathode molten pool or anode molten bath, has both avoided the waste of electrolyte, be can ensure that again
Clean environment.
Further, the heating stove overcoat holding furnace, is coated with heat insulation furnace cover plate on holding furnace；The anode molten bath passes through
Anode molten bath bearing is suspended from cathode molten pool；The exposed portion envelops of cathode bar have cathode bar coolant jacket, the sun
Rod exposed portion envelops in pole have anode stub coolant jacket；Heating furnace on the outside of the negative electrode slag outlet valve is provided with heating furnace
Dodge gate, the holding furnace on the outside of the heating furnace dodge gate is provided with holding furnace dodge gate, is easy to draw operation convenient.Described the moon
The bearing of pole molten bath bottom is used to be supported in anode molten bath, to ensure that there is cathode molten pool enough volumes to accommodate negative electrode slag,
Anode slime is avoided to mix with negative electrode slag；Cover plate is respectively provided with cathode molten pool and holding furnace, is melted with preventing electrolyte from overflowing negative electrode
Pond or holding furnace；The effect of the cathode and anode rod coolant jacket is the proper temperature of cathode and anode rod exposed part when ensureing electrolysis,
Meanwhile, be conducive to cathode and anode rod good with power supply wiring.
Further, the cathode molten pool, cathode bar, anode stub and positive plate are graphite material, and negative electrode slag outlet valve is
The graphite grazing plug of interference fit, to ensure the sealing in electrolytic process；The anode molten bath is graphite or corundum material, when adopting
When using graphite material, anode molten bath bearing is insulating refractories or anode molten bath and the insulation of anode molten bath bearing contact position pad
Refractory material backing plate, so that anode molten bath is insulated with cathode molten pool.
The operation such as charging, discharging for convenience, each part of apparatus of the present invention can be dismounted or combined.
The present invention further solves the technical scheme that its technical problem used：The method containing antimony alloy is separated, including
Following steps：
（1）Fusing contains antimony alloy：Fused salt is carried out into dispensing, is added in cathode molten pool or anode molten bath by several times, open heating
Stove heat, after fused salt is all melted, adds in anode molten bath and contains antimony alloy, and fusing contains antimony alloy；
（2）Electrolysis fused salt：Return duct is connected into cooling water, cathode bar is then connected into direct current with anode stub, carry out electricity
Solution, closes direct current after the completion of electrolysis, negative electrode slag and anode slime are discharged respectively.
Further, step（1）In, the fused salt is chloride, including sodium chloride, potassium chloride, calcium chloride, zinc chloride or chlorine
Change lead；The dispensing refers to that fused salt is divided into two groups：Two kinds or two kinds in sodium chloride, potassium chloride, calcium chloride or zinc chloride with
Upper is first group, and lead chloride is second group, and the mixing consumption of fused salt is the 20~60% of fused salt gross mass in first group, wherein, often
The 10% of the consumption >=fused salt gross mass of salt is planted, second group of consumption of lead chloride is the 40~80% of fused salt gross mass；The fused salt
Consumption be to add containing 1.5~2.0 times of antimony alloy quality.Fused salt add mode be：In cathode molten pool or anode molten bath
First group of fused salt is first added, when furnace temp reaches 680 DEG C, second group of fused salt is added, in sun after fused salt is completely dissolved
Added in the molten bath of pole and contain antimony alloy, first group of fused salt boiling point is high, second group of fused salt low boiling point, added again after after first group of fused salt melting
Entering second group of fused salt can reduce the volatilization of fused salt, it is to avoid unnecessary waste and environmental pollution.The fusing point of metallic antimony is 630.5
DEG C, as long as temperature of molten salt >=630.5 DEG C are melting contains antimony alloy.For the ease of the carrying out of molten-salt electrolysis, the fused salt face of melting
Need higher than anode molten bath.
Further, step（2）In, it is described electrolysis fused salt process in, voltage be 3~10V, anodic current density be 3000~
8000A/m2, cathode-current density is 5000~10000A/m2；The time of electrolysis is 90~180min, and the temperature of electrolysis is 680
~800 DEG C.The main chemical reactions of electrolytic process are as follows：
| Anode | Negative electrode |
The inventive method is applied to the alloy separation that electrode potential differs larger, e.g., electrode potential gap in lead-antimony alloy
The larger lead gold and silver larger with electrode potential gap in antimony, your antimony is separated with base metal.When amount of the input containing antimony alloy
When more, anode slime is suctioned out using vacuum ladle, and used vacuum ladle is existing standard part, when input contains antimony alloy
When measuring less, do not use vacuum ladle to suction out, but electrolysis and heating power supply are closed after the completion of electrolysis, open holding furnace cover plate
With cathode molten pool cover plate, molten bath is removed respectively, ingot casting.When being lead-antimony alloy containing antimony alloy, by control electric current density and
Electrolysis time and sampling analysis determine electrolysis terminal, and anode slime predominantly metallic antimony, negative electrode slag can be made to be mainly metallic lead；
When containing antimony alloy for your antimony, after electrolysis, noble metal is mainly in anode slime, negative electrode slag is the alloy of base metal, base metal
Slag further can carry out isolated various metals using other methods.
Further, when it is described containing antimony alloy for your antimony when, in step（2）In electrolytic process, the sampling point from anode melt
The content of antimony is analysed, when antimony mass content therein is 10~20%, electrolysis is completed, and the anode slime of discharge is entered into traveling one
The treatment of step, processing method is as follows：
（a）Chlorination anode slime：Anode slime is crushed, is added in hydrochloric acid solution, chlorine is passed through under stirring carries out chlorine
Change, filtering, obtain slightly golden filter residue and filtrate containing antimony；
（b）Reclaim silver, antimony：From step（a）Displacement restores elemental silver in gained filtrate containing antimony, obtains sponge silver, then will
The filtrate containing antimony gone after silver under agitation, adds reducing agent, enters line replacement reaction, and filtering obtains antimony powder and filtrate, and filtrate is concentrated to give
Chloride crude product.
When the mass content of antimony is 10~20%, be electrolysis terminal because the electrode potential of antimony be in iron, lead,
After copper, nickel, before silver, gold, in order to ensure the rate of recovery of silver, gold is high, it is necessary to control section antimony is stayed in the anode.
Further, the mass percent of main component is in your antimony：Gold 0.1~3.5%, silver 0.01~0.10% and antimony
30~40%.Also contain lead 10~40%, copper 10~20%, iron 0.5~1%, nickel 0~10%, arsenic 0.5~1% in your antimony；Antimony gold
During pyrometallurgical smelting, by preliminary concentration gold and silver, the main component containing the expensive antimony of gold and silver for obtaining is concentrate：Gold 0.05~
3.5%th, silver 0.01~0.10%, antimony 30~90%, lead 5~50%, copper 5~30%, iron 0.5~5%, nickel 0~10%, arsenic 0.5~5%,
Generally require by waving the mode of blowing, volatilize most antimony and arsenic, and by iron slag making, obtain being conducive to the expensive of later separation purification
Antimony.
Further, step（a）In, anode slime is crushed to >=20 mesh；The hydrochloric acid solution mass concentration be 15~
20wt%, anode slime is 1 with the solid-to-liquid ratio of hydrochloric acid:3~8；The quality that the chlorine is passed through is that the theory of antimony in anode slime disappears
The 94~98% of consumption, the temperature of chlorination is 25~85 DEG C, and the time of chlorination is 90~180min.Antimony in the thick golden filter residue
Content is controlled below 5%, and thick gold can be used for the raw material of deduction proof gold and fine silver；Antimony chloride, also silver chlorate are mainly in filtrate
Deng complex compound.Chlorination process main chemical reactions are as follows：
2Sb+3Cl2=2SbCl3
2Ag+Cl2=2AgCl↓
AgCl+HCl=HAgCl2
Further, step（b）In, the reducing agent is zinc powder or iron powder, and the temperature for replacing reaction is room temperature~100 DEG C,
The time for replacing reaction is 90~180min, and the quality that reducing agent is added is 1.10~1.50 times of theoretical amount.In aqueous systems
In, the electrode potential gap of silver-colored, antimony is larger, and silver can be just displaced using weak reducing agent, and antimony then needs stronger reducing agent
Can just cement out, for this reason, it may be necessary to be separately recovered silver, antimony in two steps carry out.The method for displacing silver is numerous, and the present invention is using sub-
Sulfuric acid sodium reduction silver ion obtains sponge silver；The antimony powder for finally giving can be sold as product or further ingot casting obtains essence
Antimony.The main chemical reactions of two steps displacement are as follows：
Na2SO3+2HCl=SO2+2NaCl+H2O
2HAgCl2+SO2+2H2O=2Ag↓+4HCl+H2SO4
2SbCl3+3Zn=2Sb↓+3ZnCl2
2SbCl3+3Fe=2Sb↓+3FeCl2
The course of work of apparatus of the present invention is：First negative electrode slag outlet valve is closing and sealing off, then, first group for preparing
Fused salt mixt is added in cathode molten pool or anode molten bath, installs anode stub, positive plate and cathode bar, then, the moon is covered successively
Pole molten bath cover plate, holding furnace cover plate, install return duct, loading hopper, install cathode and anode cooling jacket, by galvanic both positive and negative polarity
Connected with cathode and anode rod respectively, wouldn't power transmission, connect the power supply and power transmission of heating furnace, start to warm up, control temperature 680~
800 DEG C, the cooling water on return duct and cathode and anode cooling jacket is in turn switched on, when temperature reaches 680 DEG C, by loading hopper
Second group of fused salt is added in cathode molten pool or anode molten bath successively, is added in anode molten bath containing antimony alloy, seen by thermometric
Whether Cha Kou determines melt completely containing antimony alloy, after being melted completely containing antimony alloy, gives cathode and anode rod power transmission, proceeds by electricity
Solution, during electrolysis, it is 680~800 DEG C to keep the temperature in cathode molten pool and anode molten bath, records electrolysis time, and midway is observed
Electrolysis situation（The chemical composition of sampling analysis anode thing is also needed to when being your antimony containing antimony alloy, when the mass content of antimony is 10
It is electrolysis terminal when~20%）, direct current is closed after the completion of electrolysis, anode residue is suctioned out with vacuum ladle（When anode thing
When doses is little, the mode for removing anode molten bath is taken to discharge）, the power supply of heating furnace is disconnected, holding furnace dodge gate is opened successively
With heating furnace dodge gate, negative electrode slag outlet valve and ingot mold then are connected with splicing groove, slowly open negative electrode slag outlet valve, put
The whole molten alloy materials gone out in cathode molten pool, electrolyte fused salt is not released, and after material is discharged, negative electrode slag is closed successively and is gone out
Material valve, heating furnace dodge gate and holding furnace dodge gate.Restart heating furnace, heat up, adding appropriate second group from loading hopper melts
Salt, containing antimony alloy, into second electrolysis flow.
The principle of the inventive method is：The anode molten bath in melting molten salt electrolyte is melted in containing antimony alloy, had been electrolysed
Cheng Zhong, by the transmission of electrolyte, the foreign metal in anode pool loses electronics as ion, is transferred to negative electrode, obtains in anode
Obtain electronics and separated out in negative electrode；In the molten salt electrolyte, containing foreign metal in antimony alloy anode discharge order be iron,
Lead, copper, nickel, antimony etc., because the plumbum ion concentration balance in electrolyte is destroyed, electricity are lost containing the lead in antimony alloy in anode
Son turns into ion and enters in electrolyte, and lead reaches new balance in making electrolyte, after the lead in containing antimony alloy has been shifted, or lead
In the later stage of transfer, iron, copper, nickel, antimony progressively turn into ion, into electrolyte, reach negative electrode and obtain electronics, are separated out into negative electrode
It is alloy；The electrode potential of antimony is in after iron, lead, copper, nickel, before silver, gold, in the separation of your antimony, in order to ensure silver, gold
The rate of recovery it is high, control section antimony is stayed in the anode, because electrode potential of the gold, silver noble metal in the electrolyte is high, no
Discharge, stay in anode as anode alloy, so as to separate foreign metal, be enriched gold, silver, gold in anode alloy,
Silver, antimony electrode potential difference in aqueous are larger, by chlorination, separate remaining antimony in gold, silver alloy, further enrichment
Gold and silver, obtain thick gold, and antimony-containing solution is made antimony powder by restoring method.
The present invention mainly has the following advantages：
（1）Molten-salt electrolysis containing antimony alloy of the invention separates lead, antimony, copper etc. or is enriched with gold, silver, it is not necessary to cast positive plate or
Crush, process is simple, separation and recovery rate >=99%, the direct yield of gold, silver enrichment is up to 99.9% in your antimony, does not almost lose,
Containing the foreign metal in antimony alloy into alloy, be conducive to further recovery；
（2）Apparatus of the present invention are rational in infrastructure, and capital equipment is a set of electrolysis unit, are easy to operation, and process is simple, cost
Low, due to being mounted with return duct, the fused salt for evaporating high-temperature part returns to cathode molten pool or anode molten bath, has both reduced molten
The loss of salt, the operating environment of protection, runs safety and environmental protection again, and whole electrolytic process does not have the three wastes to produce, environment-friendly；
（3）The anode of apparatus of the present invention, negative electrode and electric wire connection point are mounted with cooling jacket, reduce the temperature of junction
Degree, protects the good contact of connecting line；
（4）Apparatus of the present invention discharge method advantages of simple, not provision for disengagement can discharge negative electrode slag and anode slime, protect
Card electrolysis is carried out continuously；
（5）Other reagents or auxiliary material need not be added during present invention process in addition to fused salt；
（6）The filtrate containing antimony your antimony recovery thick gold present invention process separates after can obtain antimony powder using substitute mode, antimony
The rate of recovery is up to 99%, and the filtrate after displacement is by being concentrated by evaporation, moreover it is possible to obtain chloride crude product, can further to valuable metal
Reclaimed, eliminated the generation of waste water；
（7）Apparatus of the present invention and technique are applied to the separation containing antimony alloy such as lead-antimony alloy, Venus regulus etc., the scope of application
It is quite varied.
Brief description of the drawings
Fig. 1 is the structural representation that the present invention separates the device embodiment containing antimony alloy；
Fig. 2 is that the present invention separates the top view containing antimony alloy device embodiment shown in Fig. 1.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
The structure that the present invention separates high lead-antimony alloy or the device embodiment of your antimony is introduced first：
As shown in figure 1, including heating furnace 1, cathode molten pool 2, anode molten bath 3, the positive plate 4 for being provided with perforate, return duct 6,
Loading hopper 7, graphite anode rod 8, negative electrode graphite rod 10 and negative electrode slag outlet valve 11, the cathode molten pool 2 and positive plate 4 are stone
Black material, negative electrode slag outlet valve 11 is the graphite grazing plug of interference fit；The cathode molten pool 2 is located in heating furnace 1, and is covered
There is cathode molten pool cover plate 5, negative electrode graphite rod 10 is accessed on the cathode molten pool cover plate 5；The anode molten bath 3 is suspended from cathode molten pool
In 2, graphite anode rod 8 passes through cathode molten pool cover plate 5, and the end of graphite anode rod 8 is fixedly connected with positive plate 4, hangs positive plate 4
In in anode molten bath 3, the positive plate 4 is disc；The return duct 6 stretches into cathode molten pool 2 through cathode molten pool cover plate 5
It is interior；The loading hopper 7 is stretched into anode molten bath 3 through cathode molten pool cover plate 5 and positive plate 4；Set on the cathode molten pool cover plate 5
There is thermometric to observe and anode slime discharging opening 9, the thermometric observation and anode slime discharging opening 9 correspond to opening on positive plate 4
Hole；The negative electrode slag outlet valve 11 is located at the bottom of cathode molten pool 2；The overcoat holding furnace 12 of the heating furnace 1, covers on holding furnace 12
There is holding furnace cover plate 13；The anode molten bath 3 is suspended from cathode molten pool 2 by anode molten bath bearing 14, anode molten bath branch
Seat 14 is insulating refractories；The exposed portion envelops of the negative electrode graphite rod 10 have negative electrode graphite rod coolant jacket 15, institute
Stating the exposed portion envelops of graphite anode rod 8 has graphite anode rod coolant jacket 16；The outside of the negative electrode slag outlet valve 11
Heating furnace is provided with heating furnace dodge gate 17, and the holding furnace in the outside of the heating furnace dodge gate 17 is provided with holding furnace dodge gate
18.Each part can be dismounted or combined.
The course of work of described device is：First negative electrode slag outlet valve 11 is closing and sealing off, then, first group for preparing
Fused salt mixt is added in cathode molten pool 2, installs graphite anode rod 8, positive plate 4 and negative electrode graphite rod 10, then, is covered successively
Cathode molten pool cover plate 5, holding furnace cover plate 13, install return duct 6, loading hopper 7, install cooled cathode water jacket 15 and anode cooling water
Set 16, galvanic both positive and negative polarity is connected with negative electrode graphite rod 10 and graphite anode rod 8 respectively, wouldn't power transmission, connection heating furnace 1
Power supply and power transmission, start to warm up, control temperature at 680~800 DEG C, in turn switch on return duct 6 and the He of cooled cathode water jacket 15
Cooling water on anode cooling jacket 16, when temperature reaches 680 DEG C, sun is added by loading hopper 7 by second group of fused salt successively
In pole molten bath 3, added in anode molten bath 3 containing antimony alloy, determine whether melt completely containing antimony alloy by thermometric observation panel 9, when
After being melted completely containing antimony alloy, to negative electrode graphite rod 10 and the power transmission of graphite anode rod 8, electrolysis is proceeded by.During electrolysis, keep
Temperature in cathode molten pool 2 and anode molten bath 3 is 680~800 DEG C, records electrolysis time, midway observation electrolysis situation（When containing antimony
Alloy also needs to the chemical composition of sampling analysis anode thing when being your antimony, when the mass content of antimony is 10~20%, be electrolysis eventually
Point）, direct current is closed after the completion of electrolysis, take the mode for removing anode molten bath to discharge, the power supply of heating furnace 1 is disconnected, beat successively
Holding furnace dodge gate 18 and heating furnace dodge gate 17 are opened, then negative electrode slag outlet valve 11 and ingot mold is connected with splicing groove, slowly
It is slow to open negative electrode slag outlet valve 11, the whole molten alloy materials in cathode molten pool 2 are released, electrolyte fused salt is not released, and works as thing
After material is discharged, negative electrode slag outlet valve 11, heating furnace dodge gate 17 and holding furnace dodge gate 18 are closed successively.Restart heating furnace 1,
Heat up, add second group of appropriate fused salt from loading hopper 7, containing antimony alloy, into second electrolysis flow.
Embodiment 1~5 introduced below separates the embodiment of the method containing antimony alloy for the present invention：
Wherein, embodiment 1 for separate high lead-antimony alloy in lead, embodiment 2~5 for separate your antimony in iron, lead, copper,
The foreign metal such as nickel and most of antimony.
The high lead-antimony alloy that the inventive method embodiment 1 is used is gained, the institute of embodiment 2~5 after the refining of high lead-antimony mining and metallurgy
Your antimony for using is that antimony gold concentrate further volatilizees obtained by blowing as pyrometallurgical smelting, the mass concentration of hydrochloric acid is 15~
20wt%, other chemical reagent unless otherwise specified, are obtained by routine business approach.
The method for separating high lead-antimony alloy：
（1）Fusing contains antimony alloy：Fused salt is carried out into dispensing, is added in cathode molten pool or anode molten bath by several times, open heating
Stove heat, after fused salt is all melted, adds in anode molten bath and contains antimony alloy, and fusing contains antimony alloy；
（2）Electrolysis fused salt：Return duct is connected into cooling water, cathode bar is then connected into direct current with anode stub, carry out electricity
Solution, closes direct current after the completion of electrolysis, negative electrode slag and anode slime are discharged respectively.
Fused salt add mode be：First group of fused salt is first added in cathode molten pool, when furnace temp reaches 680 DEG C
When, second group of fused salt is added in anode molten bath, added in anode molten bath after fused salt is completely dissolved and contain antimony alloy.Melting
Fused salt face is higher than anode molten bath.
The method for separating your antimony：
（1）Fusing contains antimony alloy：Fused salt is carried out into dispensing, is added in cathode molten pool or anode molten bath by several times, open heating
Stove heat, after fused salt is all melted, adds in anode molten bath and contains antimony alloy, and fusing contains antimony alloy；
（2）Electrolysis fused salt：Return duct is connected into cooling water, cathode bar is then connected into direct current with anode stub, carry out electricity
Solution, the content of sampling analysis antimony from anode melt, when antimony mass content therein is 10~20%, electrolysis is completed, and is closed straight
Stream electricity, negative electrode slag and anode slime are discharged respectively；The anode slime of discharge is further processed, processing method is such as
Under：
（a）Chlorination anode slime：Anode slime is crushed to >=20 mesh, is added in hydrochloric acid solution, chlorine is passed through under stirring
Gas carries out chlorination, filtering, obtains slightly golden filter residue and filtrate containing antimony；
（b）Reclaim silver, antimony：From step（a）Displacement restores elemental silver in gained filtrate containing antimony, obtains sponge silver, then will
The filtrate containing antimony gone after silver under agitation, adds zinc powder or iron powder, enters line replacement reaction, and filtering obtains antimony powder and filtrate, and filtrate is dense
Contract to obtain chloride crude product.
Fused salt add mode be：First group of fused salt is first added in cathode molten pool, when furnace temp reaches 680 DEG C
When, second group of fused salt is added in anode molten bath, added in anode molten bath after fused salt is completely dissolved and contain antimony alloy.Melting
Fused salt did not had anode molten bath.
Step（b）In, the method that the displacement restores elemental silver is：Under agitation, sodium sulfite, reaction temperature are added
It is 75~85 DEG C, the reaction time is 60min, enters line replacement, filter, obtains sponge silver and filtrate containing antimony.
High lead-antimony alloy and your antimony constituent analysis table are shown in Table 1 in embodiment 1~5, and molten salt membrane table is shown in Table 2, electrolytic condition
Parameter list is shown in Table 3.
The high lead-antimony alloy of 1 embodiment of table 1~5 and your antimony constituent analysis table
The molten salt membrane table of 2 embodiment of table 1~5
The electrolytic condition parameter list of 3 embodiment of table 1~5
The step of embodiment 1~5（2）Middle gained anode slime constituent analysis is shown in Table 4, and negative electrode slag ingredient analytical table is shown in Table 5.
The anode slime constituent analysis table of 4 embodiment of table 1~5
The negative electrode slag ingredient analytical table of 5 embodiment of table 1~5
From table 4,5, in embodiment 1, the antimony in anode is enriched with, its composition 86.49% being enriched to by
98.15%, lead 10.78% is down to 0.19% by；Antimony content in cathode alloy is 2.46%, and lead content reaches
78.59%, the antimony lead rate of recovery has reached more than 99%.
From table 4,5, in embodiment 2~5, by a molten-salt electrolysis, in anode slime, accounting of the gold in residue
It is 65~83%, the rate of recovery is up to 99.9%, and silver is also enriched with, and the rate of recovery of silver is up to 99.9%, is not contained in negative electrode slag
Gold, silver；Foreign metal in anode slime, in addition to antimony content is between 10~20%, other impurity metal contents 1.00% with
Under, being enriched in cathode alloy foreign metal more.In addition, anode slime weight is less than the 5% of your antimony weight, impurity level is small,
More other reagents will not be consumed during further gold is carried or more waste water, waste gas etc. is produced, reduced follow-up
Carry the cost of gold.
By step in embodiment 3~5（2）Gained anode slime carry out chlorination and reclaim silver, antimony treatment, the quality for the treatment of and
Its composition is shown in Table 6, wherein, the gained anode slime of embodiment 5 is divided into two parts.
The anode slime weight of 6 embodiment of table 3~5, compositional data
The step of embodiment 3~5（a）Middle chlorization condition parameter list is shown in Table 7, step（b）It is middle to reclaim silver, the conditional parameter table of antimony
8 are shown in Table, chlorination and recovery silver, antimony composition analysis table are shown in Table 9.
The anode slime chlorization condition parameter list of 7 embodiment of table 3~5
8 embodiment of table 3~5 reclaims silver, antimony conditional parameter table
The chlorination of 9 embodiment of table 3~5 and recovery silver, antimony composition analysis table
As shown in Table 9, after chlorination of anode slime, golden weight/mass percentage composition improves 9~15%, and the rate of recovery of gold is up to
99.9%, the rate of recovery of silver is up to 99.9%, meanwhile, the antimony content in thick gold filter residue drops to 2% or so, is conducive to pure gold extraction；
Filtrate containing antimony has been made antimony powder by replacing reaction, its antimony content more than 90%, the rate of recovery more than 99% of antimony.
The filtrate after antimony will be reclaimed the crude product of zinc chloride or frerrous chloride can obtain by evaporation, during do not have outside waste water
Row.Because anode slime amount is little, so, the amount of the filtrate after displacement recovery antimony and the amount of chlorate are also corresponding little.
Claims (11)
- It is 1. a kind of to separate the device containing antimony alloy, it is characterised in that：Including heating furnace, cathode molten pool, anode molten bath, it is provided with perforate Positive plate, return duct, loading hopper, anode stub, cathode bar and negative electrode slag outlet valve；The cathode molten pool is located in heating furnace, And cathode molten pool cover plate is coated with, access cathode bar on the cathode molten pool cover plate；The anode molten bath is suspended from cathode molten pool, Anode stub passes through cathode molten pool cover plate, and anode stub end is fixedly connected with positive plate, positive plate is suspended from anode molten bath；It is described Return duct is stretched into cathode molten pool through cathode molten pool cover plate；The loading hopper stretches into sun through cathode molten pool cover plate and positive plate In the molten bath of pole；The cathode molten pool cover plate is provided with thermometric observation and anode slime discharging opening, and the thermometric observation and anode are residual Slag discharging opening corresponds to the perforate on positive plate；The negative electrode slag outlet valve is located at cathode molten pool bottom.
- 2. the device containing antimony alloy is separated according to claim 1, it is characterised in that：The heating stove overcoat holding furnace, protects Heat insulation furnace cover plate is coated with warm stove；The anode molten bath is suspended from cathode molten pool by anode molten bath bearing；The cathode bar Exposed portion envelops have cathode bar coolant jacket, and the exposed portion envelops of anode stub have anode stub coolant jacket； Heating furnace on the outside of the negative electrode slag outlet valve is provided with heating furnace dodge gate, on the holding furnace on the outside of the heating furnace dodge gate It is provided with holding furnace dodge gate.
- It is 3. according to claim 1 or claim 2 to separate the device containing antimony alloy, it is characterised in that：The cathode molten pool, cathode bar, Anode stub and positive plate are graphite material, and negative electrode slag outlet valve is the graphite grazing plug of interference fit；The anode molten bath is Graphite or corundum material, when using graphite material, anode molten bath bearing is that insulating refractories or anode molten bath are melted with anode Pond bearing contact position pad insulating refractories backing plate.
- 4. a kind of one of use claims 1 to 3 described device separates the method containing antimony alloy, it is characterised in that：Including following step Suddenly：（1）Fusing contains antimony alloy：Fused salt is carried out into dispensing, is added in cathode molten pool or anode molten bath by several times, opened heating furnace and add Heat, after fused salt is all melted, adds in anode molten bath and contains antimony alloy, and fusing contains antimony alloy；The fused salt is chloride, bag Include sodium chloride, potassium chloride, calcium chloride, zinc chloride or lead chloride；The dispensing refers to that fused salt is divided into two groups：Sodium chloride, chlorination Two or more in potassium, calcium chloride or zinc chloride is first group, and lead chloride is second group, the mixing of fused salt in first group Consumption is the 20~60% of fused salt gross mass, wherein, the 10% of the consumption >=fused salt gross mass of every kind of salt, second group of use of lead chloride Measure is the 40~80% of fused salt gross mass；The consumption of the fused salt is to add 1.5~2.0 times containing antimony alloy quality；（2）Electrolysis fused salt：Return duct is connected into cooling water, cathode bar is then connected into direct current with anode stub, be electrolysed, electricity Direct current is closed after the completion of solution, negative electrode slag and anode slime are discharged respectively.
- 5. the method containing antimony alloy is separated according to claim 4, it is characterised in that：Step（2）In, the electrolysis fused salt mistake Cheng Zhong, voltage is 3~10V, and anodic current density is 3000~8000A/m2, cathode-current density is 5000~10000A/m2； The time of electrolysis is 90~180min, and the temperature of electrolysis is 680~800 DEG C.
- 6. the method containing antimony alloy is separated according to claim 4 or 5, it is characterised in that：When it is described containing antimony alloy be your antimony When, in step（2）In electrolytic process, the content of sampling analysis antimony from anode melt, when antimony mass content therein be 10~ When 20%, electrolysis is completed, and the anode slime of discharge is further processed, and processing method is as follows：（a）Chlorination anode slime：Anode slime is crushed, is added in hydrochloric acid solution, chlorine is passed through under stirring carries out chlorination, mistake Filter, obtains slightly golden filter residue and filtrate containing antimony；（b）Reclaim silver, antimony：From step（a）Displacement restores elemental silver in gained filtrate containing antimony, obtains sponge silver, then will remove silver Filtrate containing antimony afterwards under agitation, adds reducing agent, enters line replacement reaction, and filtering obtains antimony powder and filtrate, and filtrate is concentrated to give chlorination Thing crude product.
- 7. the method containing antimony alloy is separated according to claim 6, it is characterised in that：The quality of main component in your antimony Percentage is：Gold 0.1~3.5%, silver 0.01~0.10% and antimony 30~40%.
- 8. the method containing antimony alloy is separated according to claim 6, it is characterised in that：Step（a）In, anode slime is crushed To >=20 mesh；The hydrochloric acid solution mass concentration is 15~20wt%, and anode slime is 1 with the solid-liquid mass ratio of hydrochloric acid:3~8； The quality that the chlorine is passed through is the 94~98% of the theoretical consumption of antimony in anode slime, and the temperature of chlorination is 25~85 DEG C, chlorine The time of change is 90~180min.
- 9. the method containing antimony alloy is separated according to claim 7, it is characterised in that：Step（a）In, anode slime is crushed To >=20 mesh；The hydrochloric acid solution mass concentration is 15~20wt%, and anode slime is 1 with the solid-liquid mass ratio of hydrochloric acid:3~8； The quality that the chlorine is passed through is the 94~98% of the theoretical consumption of antimony in anode slime, and the temperature of chlorination is 25~85 DEG C, chlorine The time of change is 90~180min.
- 10. the method containing antimony alloy is separated according to claim 6, it is characterised in that：Step（b）In, the reducing agent is Zinc powder or iron powder, the temperature for replacing reaction are room temperature~100 DEG C, and the time for replacing reaction is 90~180min, and reducing agent is added Quality be 1.10~1.50 times of theoretical amount.
- 11. separate the method containing antimony alloy according to claim 7, it is characterised in that：Step（b）In, the reducing agent is Zinc powder or iron powder, the temperature for replacing reaction are room temperature~100 DEG C, and the time for replacing reaction is 90~180min, and reducing agent is added Quality be 1.10~1.50 times of theoretical amount.
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| CN107326400B (en) * | 2017-08-31 | 2018-11-30 | 中南大学 | A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony |
| CN108179441A (en) * | 2017-12-26 | 2018-06-19 | 广西生富锑业科技股份有限公司 | A kind of production method of high purity antimony |
| CN110429356A (en) * | 2019-07-15 | 2019-11-08 | 华中科技大学 | A kind of recovery method and device of liquid metal cell |
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| US3677926A (en) * | 1970-06-16 | 1972-07-18 | Ass Lead Mfg Ltd | Cell for electrolytic refining of metals |
| FR2692880B1 (en) * | 1992-06-29 | 1994-09-02 | Pechiney Uranium | Process for the selective electro-fluorination of alloys or metallic mixtures based on uranium. |
| CN104313643A (en) * | 2014-07-31 | 2015-01-28 | 贵州重力科技环保有限公司 | High-purity antimony producing method by two-section fused salt electrolysis method |
| CN204550728U (en) * | 2015-04-14 | 2015-08-12 | 锡矿山闪星锑业有限责任公司 | A kind of device be separated containing antimony alloy |
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