CN103320624B - Method for selectively extracting gold and silver from copper anode slime - Google Patents
Method for selectively extracting gold and silver from copper anode slime Download PDFInfo
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- CN103320624B CN103320624B CN201310281308.3A CN201310281308A CN103320624B CN 103320624 B CN103320624 B CN 103320624B CN 201310281308 A CN201310281308 A CN 201310281308A CN 103320624 B CN103320624 B CN 103320624B
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 85
- 239000004332 silver Substances 0.000 title claims abstract description 85
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000010931 gold Substances 0.000 title claims abstract description 81
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010949 copper Substances 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 85
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000605 extraction Methods 0.000 claims abstract description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 26
- 239000010802 sludge Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 8
- 229910001254 electrum Inorganic materials 0.000 claims description 7
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 claims description 7
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 239000003929 acidic solution Substances 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910001020 Au alloy Inorganic materials 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011133 lead Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical group [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- UGASTCGQAJBUOO-UHFFFAOYSA-N 3-(2-ethylhexylsulfanylmethyl)heptane Chemical compound CCCCC(CC)CSCC(CC)CCCC UGASTCGQAJBUOO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 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
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for selectively extracting gold and silver from copper anode slime, belonging to the technical field of wet metallurgy and secondary resource recovery of nonferrous metals. The method comprises the steps of: firstly, levigating copper anode slime and then extracting with a sulfuric acid solution to remove copper, filtering and washing to obtain copper-removed anode slime; then extracting gold and silver from the copper-removal anode slime through thiourea to obtain thiourea leachate; and finally placing the thiourea leachate into a diaphragm electrolytic cell for electrodepositing gold and silver, namely obtaining the gold and silver alloy on the surface of a titanium plate. According to the method, the extraction rates of gold and silver are respectively greater than 95% and 99%, the electrolytic deposition rates are respectively greater than 99.5% and 98.5%, the direct recovery rates of gold and silver are respectively greater than 94% and 96%, and the gold and silver in the copper anode slime can be effectively recovered; and the method has an entirely-wet treatment process, is lower in cost, and less in pollution to environment, and can meet the environment-friendly requirement.
Description
Technical field
The present invention relates to a kind of from copper anode mud the method for selective extraction gold and silver, belong to non-ferrous metal hydrometallurgy and secondary resource recovery technology field.
Background technology
In electrolytic refining course of copper, the insoluble component in blister copper anode is settled down to the bottom of electrolyzer as the anode sludge, when change in electrolyzer anode time, from described electrolyzer, obtain described copper anode mud.In described copper anode mud, conventionally contain copper, nickel, lead, silver, gold, selenium, tellurium, arsenic, antimony, bismuth and a small amount of platinum metals etc.At present, copper anode mud is processed still taking traditional thermal process as main both at home and abroad, because its operating environment is poor, seriously polluted, the production cycle long, valuable metal is difficult for the problems such as comprehensive utilization and faces the challenge.In addition, thermal process is concerning medium-sized and small enterprises, and investment is large, plant factor is low, plumbous evil is difficult to resolve certainly.Therefore, adopt the method for hydrometallurgy selective recovery gold and silver from copper anode mud is the important topic in copper anode mud treating processes always.
July 16 in 1986 Zhong state invention application publication number CN85100108, Tsing-Hua University's Huating booth and Xi Deli invention " from the anode mud of copper electroplating, extracting the extraction process of gold and silver " disclosed, technical process with the processing copper anode mud of two (2-ethylhexyl) thioether extraction gold and silver has been proposed, comprise following master operation: material pre-treatment, nitric acid Leaching of Silver, silver is extracted in extraction, and chloroazotic acid leaches nitric acid and soaks the gold in silver-colored slag, and gold is extracted in extraction.This patent application need be soaked silver with nitric acid and be soaked gold with chloroazotic acid, in two kinds of leach liquors, impurity is a lot, although gold and silver can be separated with most of impurity through extraction, but bring certain trouble for the recovery of other valuable elements in leach liquor and the purification of extraction agent, and thioether kind of extractants taste used is smelly, and operating environment is bad.
September 10 in 1997 Zhong state invention application publication number CN1158905, people's inventions such as the poplar Zong Rong of Kunming Institute of Precious Metals " extracting the method for gold and silver and valuable metal from the high arsenic-and copper-bearing anode sludge " disclosed, proposition comprises and utilizes NaOH to leach the high arsenic-and copper-bearing anode sludge, and from solution, extract recovery with composite extractant golden, it is characterized in that the anode sludge is 1:(8～20 in solid-to-liquid ratio), under 80～90 DEG C of conditions of temperature, with the NaOH solution leaching of 100～300g/L, to remove arsenic, lead, then utilize already known processes comprehensive recovery of gold silver and other valuable metal.This patent of invention is mainly before reclaiming gold and silver by ordinary method, with the most of arsenic of NaOH solution Leaching Removal, the lead of higher concentration, in the slag of gained dearsenification, lead, generally all also has 2%～5% lead, arsenic, antimony, in addition in the anode sludge, 99% copper is still retained in slag, therefore little for follow-up ordinary method comprehensive recovery of gold silver and other valuable metal improvement effects.
March 13 in 2012 Zhong state invention application publication number 201210475657.4, disclose " a kind of method of gold and silver in selective recovery copper anode mud " that the deep little dragon in Chenzhou City Jingui Silver Industry Co., Ltd waits people to invent, propose under high-temperature and high-pressure conditions, with weakly acidic ammonium thiocyanate or sodium thiocyanate solution, the gold and silver in copper anode mud is carried out to selectivity leaching, it is characterized in that copper anode mud is below 300 orders through being milled to granularity, the liquid-solid ratio of the anode sludge and leaching agent is (5～7): 1mL/g, the concentration that selectivity leaches agent ammonium thiocyanate or sodium thiocyanate solution is 80～100g/L, sulfuric acid concentration is 0.2～0.5mol/L, pH is 1～3, leaching pressure is 0.5～1.5MPa, 120～200 DEG C of extraction temperatures, reaction times 2～6h.Gained leach liquor is adjusted different pH values with sodium bicarbonate and sulfuric acid respectively and is carried out twice removal of impurities, filtration, adds the heavy silver of sodium-chlor in the Concentration of Gold silvering solution obtaining, and ammonia solvent-hydrazine hydrate reduction obtains silver; After heavy silver, liquid obtains bronze with zinc dust precipitation.Be respectively more than 90% and 94% from copper anode mud to the direct yield that obtains respectively bronze, silver powder.This inventive method leaches gold and silver energy selectivity simultaneously, but leaching process need with High Temperature High Pressure, leach liquor must be through twice removal of impurities and filtration, still need to use the relatively large plurality of reagents such as ammoniacal liquor and hydrazine hydrate, processing step is more, gained gold and silver still needs purification processes.
Summary of the invention
The present invention is exactly problem and the deficiency existing for above-mentioned prior art, provide a kind of from copper anode mud the method for selective extraction gold and silver.The leaching yield of the method gold and silver is greater than respectively 95% and 99%, electrolytic deposition rate is greater than respectively 99.5% and 98.5%, gold and silver direct yield is greater than respectively 94% and 96%, can more effectively reclaim the gold and silver in copper anode mud, and the method is full wet processing process, cost is lower, to the less pollution of environment, meets environmental requirement.
A method for selective extraction gold and silver from copper anode mud, concrete steps are as follows:
(1) by levigate copper anode mud to granularity be 200～300 orders, then join in sulphuric acid soln for (3～5): 1mL/g according to liquid-solid ratio, under the condition of room temperature, drum pneumatic blending, leach 16～24h, then after filtration, after washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return to cupric electrolysis production process;
(2) decopper(ing) anode sludge step (1) being obtained is according to liquid-solid ratio (10～20): 1mL/g joins in thiourea solution, add again oxygenant to obtain mixing liquid, under 0.5～1.5 condition, leach 16～24h taking extraction temperature as 30～60 DEG C, pH, then after filtration, after washing, obtain Leaching In Thiourea Solutions fluid and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein;
(3) the Leaching In Thiourea Solutions fluid obtaining in step (2) is joined to the cathodic area of diaphragm sell, pH is that 0.5～1.5 acidic solution joins positive column, taking titanium plate as negative electrode, lead-silver alloys plate is anode, is that 30～50 DEG C, cathode current density are 5～50A/m at electrolyte temperature
2electrolytic deposition 10～15h under condition, obtains electrum on titanium plate surface.
The copper anode mud of described step (1) comprises the component of following mass percent: silver 5%～25%, gold 0.05%～2.0%, selenium 3%～10%, tellurium 0.3%～1.0%, copper 13%～25%.
Sulfuric acid is the mixture of the vitriol oil and water in described step (1), and wherein vitriol oil consumption is 1.2～1.5 times of theoretical consumption of sulfuric acid and copper complete reaction, and the vitriol oil is analytical pure.
In described step (1), leach for one or more snippets leaches, until the copper content in the decopper(ing) anode sludge is less than 1%.
Thiourea concentration in described step (2) is 30～70g/L.
Oxygenant in described step (2) comprises Fe
3+and/or H
2o
2, the ratio of its add-on and mixing liquid is 2～10:1g/L.
In described step (2), leach for multistage leaches, until the leaching yield of gold and silver is greater than respectively 95% and 99%.
Barrier film in diaphragm sell in described step (3) is cationic exchange membrane.
In described step (3), in lead-silver alloys plate, silver content is 1wt%.
In described step (3), acidic solution is the mixed solution of sulfuric acid or sulfuric acid and nitric acid.
The pH of step (2) regulates by acid, and acid is sulfuric acid and/or nitric acid.
Galvanic deposit in described step (3) is finished react rear remaining electrodeposition tail washings (remaining Leaching In Thiourea Solutions fluid in cathodic area) and carry out ion exchange resin and adsorb after residual gold and silver, adsorption tail liquid is adjusted and returned to step (2) after thiourea concentration to 30～70g/L and continue leaching gold and silver.
Beneficial effect of the present invention and advantage are:
(1) the sour sulfur urea solution that the present invention adopts optionally leaches the gold and silver in the decopper(ing) anode sludge under nearly room temperature condition simultaneously, obtains the infusion solution that contains gold and silver, and the leaching yield of gold and silver is greater than respectively 95% and 99%.
(2) the Leaching In Thiourea Solutions fluid that contains gold and silver that the present invention obtains can, through diaphragm electrolysis deposition, be deposited on gold and silver on negative electrode simultaneously, obtains electrum, and gold and silver electrolytic deposition rate is greater than respectively 99.5% and 98.5%.
(3) the present invention obtains electrum from the decopper(ing) anode sludge to electrolytic deposition, and the direct yield of gold and silver can be greater than respectively 94% and 96%.
(4) when the present invention leaches gold and silver with sour sulfur urea solution, rare metal selenium, tellurium etc. are not leached and are enriched in the leached mud of gold and silver, be conducive to subsequent technique the extraction of the rare elements such as selenium, tellurium in described gold and silver leaching slag is reclaimed.
(5) the present invention is full wet processing process, compared with current technology, do not produce harmful flue dust, do not form the slag containing gold and silver, shorten technical process and activity duration, can reduce energy consumption and the production cost of copper anode mud processing, made gold and silver obtain efficient recovery, less pollution to environment, meets environmental requirement simultaneously.
Brief description of the drawings
Fig. 1 is the process flow sheet of the present invention's method of selective extraction gold and silver from copper anode mud.
Embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the method for the present invention's selective extraction gold and silver from copper anode mud is described further.
Embodiment 1
If Fig. 1 is as shown in the process flow sheet of the method for selective extraction gold and silver copper anode mud:
(1) 150g copper anode mud (is comprised to the component of following mass percent: silver 5%, gold 0.05%, selenium 3%, tellurium 0.3%, copper 13%) levigate to granularity be 200 orders, then be that 3:1mL/g joins in sulphuric acid soln according to liquid-solid ratio, wherein sulfuric acid is the mixture of the vitriol oil and water, vitriol oil consumption is 1.2 times of theoretical consumption of sulfuric acid and copper complete reaction, the vitriol oil is analytical pure, in room temperature, under the condition of drum pneumatic blending, leach 16h, then after filtration, after washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return to cupric electrolysis production process, in this step, decopper(ing) anode cement copper content is 5.1%, need carry out two sections leaches until the copper content in the decopper(ing) anode sludge is less than 1%,
(2) decopper(ing) anode sludge step (1) being obtained joins in 30g/L thiourea solution according to liquid-solid ratio 10:1mL/g, then adds 3g to contain Fe
3+oxygenant obtains mixing liquid, wherein the ratio of oxygenant add-on and mixing liquid is 2:1g/L, taking extraction temperature as 30 DEG C, with sulfuric acid adjust pH under 0.5 condition, leach 16h, then after filtration, after washing, obtain Leaching In Thiourea Solutions fluid and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, and in this step, the leaching yield of gold and silver is respectively 79.5% and 56.7%, need carry out two sections and leach until the leaching yield of gold and silver is greater than respectively 95% and 99%;
(3) the Leaching In Thiourea Solutions fluid obtaining in step (2) is joined to the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 0.5 sulphuric acid soln joins positive column, taking titanium plate as negative electrode, silver content is that lead-silver alloys plate of 1wt% is anode, is that 30 DEG C, cathode current density are 5A/m at electrolyte temperature
2electrolytic deposition 10h under condition, obtains electrum 8.5g on titanium plate surface, and in this step, the electrolytic deposition rate of gold and silver is respectively 99.6% and 98.5%.Galvanic deposit in described step (3) is finished react rear remaining electrodeposition tail washings (remaining Leaching In Thiourea Solutions fluid in cathodic area) and carry out ion exchange resin and adsorb after residual gold and silver, adsorption tail liquid is adjusted to thiourea concentration and continue leaching gold and silver to returning to step (2) after 30g/L.
Embodiment 2
If Fig. 1 is as shown in the process flow sheet of the method for selective extraction gold and silver copper anode mud, from copper anode mud, the concrete steps of the method for selective extraction gold and silver are as follows: (1) (comprises the component of following mass percent: silver 25% by 150g copper anode mud, gold 2.0%, selenium 10%, tellurium 1.0%, copper 25%) levigate to granularity be 300 orders, then be that 5:1mL/g joins in sulphuric acid soln according to liquid-solid ratio, wherein sulfuric acid is the mixture of the vitriol oil and water, vitriol oil consumption is 1.5 times of theoretical consumption of sulfuric acid and copper complete reaction, the vitriol oil is analytical pure, in room temperature, under the condition of drum pneumatic blending, leach 24h, then after filtration, after washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return to cupric electrolysis production process, in this step, decopper(ing) anode cement copper content is 0.89%, do not need to carry out multistage leaching,
(2) decopper(ing) anode sludge step (1) being obtained joins in 70g/L thiourea solution according to liquid-solid ratio 20:1mL/g, then adds 30g oxygenant to obtain mixing liquid, and wherein oxygenant comprises Fe
3+and H
2o
2the ratio of oxygenant add-on and mixing liquid is 10:1g/L, under 1.5 condition, leach 24h taking extraction temperature as 60 DEG C, pH, the wherein sulfuric acid of volume ratio 1:1 and the mixing acid adjustment of nitric acid for pH, then after filtration, washing after, obtain Leaching In Thiourea Solutions fluid and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, in this step, the leaching yield of gold and silver is respectively 62.8% and 70.3%, need carry out two sections and leach until the leaching yield of gold and silver is greater than respectively 95% and 99%;
(3) the Leaching In Thiourea Solutions fluid obtaining in step (2) is joined to the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 1.5 acidic solution joins positive column, wherein acidic solution is the sulfuric acid of volume ratio 1:1 and the mixed solution of nitric acid, taking titanium plate as negative electrode, silver content is that lead-silver alloys plate of 1wt% is anode, is that 50 DEG C, cathode current density are 50A/m at electrolyte temperature
2electrolytic deposition 15h under condition, obtains electrum 41.4g on titanium plate surface, and in this step, the electrolytic deposition rate of gold and silver is respectively 99.8% and 98.8%.Galvanic deposit in described step (3) is finished react rear remaining electrodeposition tail washings (remaining Leaching In Thiourea Solutions fluid in cathodic area) and carry out ion exchange resin and adsorb after residual gold and silver, adsorption tail liquid is adjusted to thiourea concentration and continue leaching gold and silver to returning to step (2) after 70g/L.
Embodiment 3
If Fig. 1 is as shown in the process flow sheet of the method for selective extraction gold and silver copper anode mud:
(1) 150g copper anode mud (is comprised to the component of following mass percent: silver 18%, gold 1.0%, selenium 5%, tellurium 0.8%, copper 20%) levigate to granularity be 250 orders, then be that 4:1mL/g joins in sulphuric acid soln according to liquid-solid ratio, wherein sulfuric acid is the mixture of the vitriol oil and water, vitriol oil consumption is 1.3 times of theoretical consumption of sulfuric acid and copper complete reaction, the vitriol oil is analytical pure, in room temperature, under the condition of drum pneumatic blending, leach 20h, then after filtration, after washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return to cupric electrolysis production process, in this step, decopper(ing) anode cement copper content is 0.91%, do not need to carry out multistage leaching,
(2) decopper(ing) anode sludge step (1) being obtained joins in 50g/L thiourea solution according to liquid-solid ratio 15:1mL/g, then adds 9g to contain Fe
3+oxygenant obtains mixing liquid, wherein the ratio of oxygenant add-on and mixing liquid be 4:1g/L taking extraction temperature as 40 DEG C, adjust pH to leach 20h under 1.0 condition with sulfuric acid, then after filtration, after washing, obtain Leaching In Thiourea Solutions fluid and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, in this step, the leaching yield of gold and silver is respectively 51.2% and 60.7%, need carry out two sections and leach until the leaching yield of gold and silver is greater than respectively 95% and 99%;
(3) the Leaching In Thiourea Solutions fluid obtaining in step (2) is joined to the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 1.0 sulphuric acid soln joins positive column, taking titanium plate as negative electrode, silver content is that lead-silver alloys plate of 1wt% is anode, is that 40 DEG C, cathode current density are 20A/m at electrolyte temperature
2electrolytic deposition 12h under condition, obtains electrum 29.6g on titanium plate surface, and in this step, the electrolytic deposition rate of gold and silver is respectively 99.7% and 98.7%.Galvanic deposit in described step (3) is finished react rear remaining electrodeposition tail washings (remaining Leaching In Thiourea Solutions fluid in cathodic area) and carry out ion exchange resin and adsorb after residual gold and silver, adsorption tail liquid is adjusted to thiourea concentration and continue leaching gold and silver to returning to step (2) after 50g/L.
Claims (9)
1. a method for selective extraction gold and silver from copper anode mud, is characterized in that concrete steps are as follows:
(1) by levigate copper anode mud to granularity be 200～300 orders, then join in sulphuric acid soln for (3～5): 1mL/g according to liquid-solid ratio, under the condition of room temperature, drum pneumatic blending, leach 16～24h, then after filtration, after washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return to cupric electrolysis production process;
(2) decopper(ing) anode sludge step (1) being obtained is according to liquid-solid ratio (10～20): 1mL/g joins in thiourea solution, add again oxygenant to obtain mixing liquid, under 0.5～1.5 condition, leach 16～24h taking extraction temperature as 30～60 DEG C, pH, then after filtration, after washing, obtain Leaching In Thiourea Solutions fluid and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein;
(3) the Leaching In Thiourea Solutions fluid obtaining in step (2) is joined to the cathodic area of diaphragm sell, pH is that 0.5～1.5 acidic solution joins positive column, taking titanium plate as negative electrode, lead-silver alloys plate is anode, is that 30～50 DEG C, cathode current density are 5～50A/m at electrolyte temperature
2electrolytic deposition 10～15h under condition, obtains electrum on titanium plate surface.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: the copper anode mud of described step (1) comprises the component of following mass percent: silver 5%～25%, gold 0.05%～2.0%, selenium 3%～10%, tellurium 0.3%～1.0%, copper 13%～25%.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: sulfuric acid is the mixture of the vitriol oil and water in described step (1), wherein vitriol oil consumption is 1.2～1.5 times of theoretical consumption of sulfuric acid and copper complete reaction.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: the thiourea concentration in described step (2) is 30～70g/L.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: the oxygenant in described step (2) comprises Fe
3+and/or H
2o
2, the ratio of its add-on and mixing liquid is 2～10:1g/L.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: in described step (2), leach for multistage leaching, until the leaching yield of gold and silver is greater than respectively 95% and 99%.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: the barrier film in described step (3) septation electrolyzer is cationic exchange membrane.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: in described step (3), in lead-silver alloys plate, silver content is 1wt%.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: in described step (3), acidic solution is the mixed solution of sulfuric acid or sulfuric acid and nitric acid.
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| CN108239703B (en) * | 2016-12-23 | 2019-09-03 | 有研工程技术研究院有限公司 | A kind of electrochemical method and equipment controlling bioleaching process |
| CN107674992B (en) * | 2017-09-21 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of cleaning extracting method of metallic silver |
| CN111607698B (en) * | 2019-02-25 | 2022-09-16 | 中国瑞林工程技术股份有限公司 | Method for treating copper anode slime |
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| JPS53116220A (en) * | 1977-03-23 | 1978-10-11 | Furukawa Electric Co Ltd:The | Separating method for copper from copper electrolysis anode slime |
| JPS5952696B2 (en) * | 1978-03-11 | 1984-12-21 | 古河電気工業株式会社 | Method for recovering copper and selenium from copper electrolysis anode slime |
| US4283224A (en) * | 1980-05-05 | 1981-08-11 | Southwire Company | Separative treatment of anode slime |
| WO2003080879A1 (en) * | 2002-03-26 | 2003-10-02 | Council Of Scientific And Industrial Research | Process for the recovery of gold and silver from used refractory bricks |
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| CN102943180B (en) * | 2012-07-20 | 2014-07-02 | 北京科技大学 | Method for recycling gold and silver from silver separating residues of copper anode slime |
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