CN103320624A - 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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- CN103320624A CN103320624A CN2013102813083A CN201310281308A CN103320624A CN 103320624 A CN103320624 A CN 103320624A CN 2013102813083 A CN2013102813083 A CN 2013102813083A CN 201310281308 A CN201310281308 A CN 201310281308A CN 103320624 A CN103320624 A CN 103320624A
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 89
- 239000004332 silver Substances 0.000 title claims abstract description 89
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010931 gold Substances 0.000 title claims abstract description 83
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 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 34
- 238000005406 washing Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 37
- 239000007788 liquid Substances 0.000 claims description 27
- 239000010802 sludge Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 12
- 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
- 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
- 238000006243 chemical reaction Methods 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
- 239000003792 electrolyte Substances 0.000 claims description 5
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 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 9
- 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 6
- 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
- 238000010521 absorption reaction Methods 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
- 239000002893 slag Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 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
- 241000409201 Luina Species 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
- 238000000498 ball milling Methods 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
- 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
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 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
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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 the blister copper anode is settled down to the bottom of electrolyzer as the anode sludge, during anode in changing electrolyzer, obtains described copper anode mud from described electrolyzer.In described copper anode mud, contain copper, nickel, lead, silver, gold, selenium, tellurium, arsenic, antimony, bismuth and a spot of platinum metals etc. usually.At present, copper anode mud is handled still based on traditional thermal process both at home and abroad, because problems such as its operating environment is poor, seriously polluted, the production cycle long, valuable metal is difficult for comprehensive utilization face the challenge.In addition, thermal process is concerning medium-sized and small enterprises, and investment is big, plant factor is low, plumbous evil is difficult to resolve and determines.Therefore, the method for employing hydrometallurgy selective recovery gold and silver from copper anode mud is the important topic in the copper anode mud treating processes always.
State's invention application publication number CN85100108 in 16 days July in 1986, Tsing-Hua University's Huating booth and Xi Deli invention " extracting the extraction process of gold and silver from the anode mud of copper electroplating " 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: the material pre-treatment, nitric acid leaches silver, silver is extracted in extraction, and chloroazotic acid leaching nitric acid soaks the gold in the silver-colored slag, and gold is extracted in extraction.This patent application needs to soak silver with nitric acid and soaks gold with chloroazotic acid, impurity is a lot of in two kinds of leach liquors, though gold and silver can be separated with most of impurity through extraction, but bring certain trouble for the recovery of other valuable elements in the leach liquor and the purification of extraction agent, and used thioether kind of extractants flavor is smelly, and operating environment is bad.
State's invention application publication number CN1158905 in 10 days September in 1997, people such as the poplar Zong Rong of Kunming Institute of Precious Metals invention " 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 extract from solution with composite extractant and to reclaim gold, it is characterized in that the anode sludge is 1:(8～20 in solid-to-liquid ratio), under 80～90 ℃ of conditions of temperature, NaOH solution with 100～300g/L leaches, to remove arsenic, lead, utilize already known processes comprehensive recovery of gold silver and other valuable metal then.This patent of invention mainly is before reclaiming gold and silver with ordinary method, NaOH solution leaching with higher concentration removes most of arsenic, lead, generally all also has 2%～5% lead, arsenic, antimony in the slag of gained dearsenification, lead, 99% copper still is retained in the slag in the anode sludge in addition, and is therefore little for follow-up ordinary method comprehensive recovery of gold silver and other valuable metal improvement effects.
State's invention application publication number 201210475657.4 in 13 days March in 2012, " method of gold and silver in a kind of selective recovery copper anode mud " of people's inventions such as the deep little dragon in Chenzhou City Jingui Silver Industry Co., Ltd disclosed, proposition is under high-temperature and high-pressure conditions, with weakly acidic ammonium thiocyanate or sodium thiocyanate solution the gold and silver in the copper anode mud being carried out selectivity leaches, it is characterized in that copper anode mud is below 300 orders through ball milling 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 ℃ of extraction temperatures, reaction times 2～6h.The 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 enrichment gold and silver liquid that obtains, and ammonia solvent-hydrazine hydrate reduction obtains silver; Heavy silver back liquid obtains bronze with zinc dust precipitation.Be respectively more than 90% and 94% from copper anode mud to the direct yield that obtains bronze, silver powder respectively.This inventive method can selectivity leaches simultaneously to gold and silver, but leaching process need with High Temperature High Pressure, leach liquor must be through twice removal of impurities and filtration, still need use plurality of reagents such as relatively large ammoniacal liquor and hydrazine hydrate, processing step is more, the gained gold and silver still needs purification processes.
Summary of the invention
The present invention is exactly problem and the deficiency that exists at above-mentioned prior art, provide a kind of from copper anode mud the method for selective extraction gold and silver.The leaching yield of these method gold and silver is respectively greater than 95% and 99%, the electrolytic deposition rate is respectively greater than 99.5% and 98.5%, the gold and silver direct yield is respectively greater than 94% and 96%, can more effectively reclaim the gold and silver in the copper anode mud, and this method is full wet processing process, cost is lower, and is less to the pollution of environment, compliance with environmental protection requirements.
A kind of from copper anode mud the method for selective extraction gold and silver, concrete steps are as follows:
(1) with copper anode mud levigate to granularity be 200～300 orders, join in the sulphuric acid soln for (3～5): 1mL/g according to liquid-solid ratio then, under the condition of room temperature, drum pneumatic blending, leach 16～24h, then after filtration, after the washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return the cupric electrolysis production process;
(2) the decopper(ing) anode sludge that step (1) is obtained is according to liquid-solid ratio (10～20): 1mL/g joins in the thiourea solution, add oxygenant again and obtain mixing liquid, be that 30～60 ℃, pH are to leach 16～24h under 0.5～1.5 the condition with extraction temperature, then after filtration, after the washing, obtain thiocarbamide leach liquor and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein;
(3) the thiocarbamide leach liquor that obtains in the step (2) is joined the cathodic area of diaphragm sell, pH is that 0.5～1.5 acidic solution joins the positive column, be negative electrode with the titanium plate, lead-silver alloys plate is anode, is that 30～50 ℃, cathode current density are 5～50A/m at electrolyte temperature
2Electrolytic deposition 10～15h under the condition namely obtains electrum on titanium plate surface.
The copper anode mud of described step (1) comprises following component by 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 the 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.
Leach in the described step (1) to one or more snippets leaches, the copper content in the decopper(ing) anode sludge is less than 1%.
Thiourea concentration in the described step (2) is 30～70g/L.
Oxygenant in the 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.
Leach in the described step (2) and be the multistage leaching, up to the leaching yield of gold and silver respectively greater than 95% and 99%.
Barrier film in the diaphragm sell in the described step (3) is cationic exchange membrane.
Silver content is 1wt% in lead in the described step (3)-silver alloys plate.
Acidic solution is the mixed solution of sulfuric acid or sulfuric acid and nitric acid in the described step (3).
The pH of step (2) regulates by acid, and acid is sulfuric acid and/or nitric acid.
After galvanic deposit in the described step (3) finished reaction and finish back remaining electrodeposition tail washings (remaining thiocarbamide leach liquor in the cathodic area) and carry out the residual gold and silver of ion exchange resin absorption, adsorption tail liquid adjusted return step (2) behind thiourea concentration to 30～70g/L and continue the leaching gold and silver.
Beneficial effect of the present invention and advantage are:
(1) the sour sulfur urea solution of the present invention's employing is optionally leaching simultaneously to the gold and silver in the decopper(ing) anode sludge under nearly room temperature condition, obtains to contain the infusion solution of gold and silver, and the leaching yield of gold and silver is respectively greater than 95% and 99%.
(2) the thiocarbamide leach liquor that contains gold and silver that the present invention obtains can be deposited on gold and silver on the negative electrode simultaneously through the diaphragm electrolysis deposition, obtains electrum, and gold and silver electrolytic deposition rate is respectively greater than 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 respectively greater than 94% and 96%.
When (4) the present invention leached gold and silver with the sour sulfur urea solution, rare metal selenium, tellurium etc. were not leached and are enriched in the leached mud of gold and silver, be conducive to subsequent technique the extraction of rare elements such as selenium, tellurium in the described gold and silver leached mud is reclaimed.
(5) the present invention is full wet processing process, compare with current technology, do not produce harmful flue dust, do not form the slag that contains gold and silver, shortened technical process and activity duration, can reduce energy consumption and production cost that copper anode mud is handled, made gold and silver obtain efficient recovery, less to the pollution of environment simultaneously, compliance with environmental protection requirements.
Description of 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
As Fig. 1 from shown in the process flow sheet of the method for selective extraction gold and silver the copper anode mud:
(1) the 150g copper anode mud (is comprised following component by mass percent: silver 5%, gold 0.05%, selenium 3%, tellurium 0.3%, copper 13%) levigate to granularity be 200 orders, be that 3:1mL/g joins in the sulphuric acid soln according to liquid-solid ratio then, 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, leach 16h under the condition of drum pneumatic blending, then after filtration, after the washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return the cupric electrolysis production process, decopper(ing) anode cement copper content is 5.1% in this step, need carry out the copper content of two sections leachings in the decopper(ing) anode sludge less than 1%;
(2) the decopper(ing) anode sludge that step (1) is obtained joins in the 30g/L thiourea solution according to liquid-solid ratio 10:1mL/g, adds 3g again and contains Fe
3+Oxygenant obtains mixing liquid, wherein the ratio of oxygenant add-on and mixing liquid is 2:1g/L, be 30 ℃, transfer pH to leach 16h under 0.5 the condition with sulfuric acid with extraction temperature, then after filtration, after the washing, obtain thiocarbamide leach liquor and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, and the leaching yield of gold and silver is respectively 79.5% and 56.7% in this step, need carry out two sections leachings up to the leaching yield of gold and silver respectively greater than 95% and 99%;
(3) the thiocarbamide leach liquor that obtains in the step (2) is joined the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 0.5 sulphuric acid soln joins the positive column, be negative electrode with the titanium plate, silver content is that lead-silver alloys plate of 1wt% is anode, is that 30 ℃, cathode current density are 5A/m at electrolyte temperature
2Electrolytic deposition 10h under the condition namely obtains electrum 8.5g on titanium plate surface, and the electrolytic deposition rate of gold and silver is respectively 99.6% and 98.5% in this step.After remaining electrodeposition tail washings (remaining thiocarbamide leach liquor in the cathodic area) carried out the residual gold and silver of ion exchange resin absorption after middle galvanic deposit end was reacted and finished to described step (3), adsorption tail liquid is adjusted thiourea concentration to 30g/L, return step (2) continuation leaching gold and silver.
Embodiment 2
As Fig. 1 from shown in the process flow sheet of the method for selective extraction gold and silver the copper anode mud, the concrete steps of the method for selective extraction gold and silver are as follows from copper anode mud: (1) (comprises following component by mass percent: silver 25% with the 150g copper anode mud, gold 2.0%, selenium 10%, tellurium 1.0%, copper 25%) levigate to granularity be 300 orders, be that 5:1mL/g joins in the sulphuric acid soln according to liquid-solid ratio then, 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, leach 24h under the condition of drum pneumatic blending, then after filtration, after the washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return the cupric electrolysis production process, and decopper(ing) anode cement copper content is 0.89% in this step, need not carry out multistage and leach;
(2) the decopper(ing) anode sludge that step (1) is obtained joins in the 70g/L thiourea solution according to liquid-solid ratio 20:1mL/g, adds the 30g oxygenant again and obtains mixing liquid, and wherein oxygenant comprises Fe
3+And H
2O
2The ratio of oxygenant add-on and mixing liquid is 10:1g/L, be that 60 ℃, pH are to leach 24h under 1.5 the condition with extraction temperature, the wherein pH sulfuric acid of volume ratio 1:1 and the mixing acid adjustment of nitric acid, then after filtration, the washing after, obtain thiocarbamide leach liquor and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, the leaching yield of gold and silver is respectively 62.8% and 70.3% in this step, need carry out two sections leachings up to the leaching yield of gold and silver respectively greater than 95% and 99%;
(3) the thiocarbamide leach liquor that obtains in the step (2) is joined the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 1.5 acidic solution joins the positive column, wherein acidic solution is the sulfuric acid of volume ratio 1:1 and the mixed solution of nitric acid, be negative electrode with the titanium plate, silver content is that lead-silver alloys plate of 1wt% is anode, is that 50 ℃, cathode current density are 50A/m at electrolyte temperature
2Electrolytic deposition 15h under the condition namely obtains electrum 41.4g on titanium plate surface, and the electrolytic deposition rate of gold and silver is respectively 99.8% and 98.8% in this step.After remaining electrodeposition tail washings (remaining thiocarbamide leach liquor in the cathodic area) carried out the residual gold and silver of ion exchange resin absorption after middle galvanic deposit end was reacted and finished to described step (3), adsorption tail liquid is adjusted thiourea concentration to 70g/L, return step (2) continuation leaching gold and silver.
Embodiment 3
As Fig. 1 from shown in the process flow sheet of the method for selective extraction gold and silver the copper anode mud:
(1) the 150g copper anode mud (is comprised following component by mass percent: silver 18%, gold 1.0%, selenium 5%, tellurium 0.8%, copper 20%) levigate to granularity be 250 orders, be that 4:1mL/g joins in the sulphuric acid soln according to liquid-solid ratio then, wherein sulfuric acid is the mixture of the vitriol oil and water, and vitriol oil consumption is 1.3 times of theoretical consumption of sulfuric acid and copper complete reaction, and the vitriol oil is analytical pure, in room temperature, leach 20h under the condition of drum pneumatic blending, then after filtration, after the washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return the cupric electrolysis production process, decopper(ing) anode cement copper content is 0.91% in this step, need not carry out multistage and leach;
(2) the decopper(ing) anode sludge that step (1) is obtained joins in the 50g/L thiourea solution according to liquid-solid ratio 15:1mL/g, adds 9g again and contains Fe
3+Oxygenant obtains mixing liquid, wherein to be 4:1g/L be 40 ℃, transfer pH to leach 20h under 1.0 the condition with sulfuric acid with extraction temperature the ratio of oxygenant add-on and mixing liquid, then after filtration, after the washing, obtain thiocarbamide leach liquor and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein, the leaching yield of gold and silver is respectively 51.2% and 60.7% in this step, need carry out two sections leachings up to the leaching yield of gold and silver respectively greater than 95% and 99%;
(3) the thiocarbamide leach liquor that obtains in the step (2) is joined the cathodic area of diaphragm sell (barrier film is cationic exchange membrane), pH is that 1.0 sulphuric acid soln joins the positive column, be negative electrode with the titanium plate, silver content is that lead-silver alloys plate of 1wt% is anode, is that 40 ℃, cathode current density are 20A/m at electrolyte temperature
2Electrolytic deposition 12h under the condition namely obtains electrum 29.6g on titanium plate surface, and the electrolytic deposition rate of gold and silver is respectively 99.7% and 98.7% in this step.After remaining electrodeposition tail washings (remaining thiocarbamide leach liquor in the cathodic area) carried out the residual gold and silver of ion exchange resin absorption after middle galvanic deposit end was reacted and finished to described step (3), adsorption tail liquid is adjusted thiourea concentration to 50g/L, return step (2) continuation leaching gold and silver.
Claims (10)
1. the method for a selective extraction gold and silver from copper anode mud is characterized in that concrete steps are as follows:
(1) with copper anode mud levigate to granularity be 200～300 orders, join in the sulphuric acid soln for (3～5): 1mL/g according to liquid-solid ratio then, under the condition of room temperature, drum pneumatic blending, leach 16～24h, then after filtration, after the washing, obtain the decopper(ing) anode sludge and copper sulfate leaching liquid, copper sulfate leaching liquid can return the cupric electrolysis production process;
(2) the decopper(ing) anode sludge that step (1) is obtained is according to liquid-solid ratio (10～20): 1mL/g joins in the thiourea solution, add oxygenant again and obtain mixing liquid, be that 30～60 ℃, pH are to leach 16～24h under 0.5～1.5 the condition with extraction temperature, then after filtration, after the washing, obtain thiocarbamide leach liquor and rich selen-tellurjum leached mud, rich selen-tellurjum leached mud can reclaim selen-tellurjum wherein;
(3) the thiocarbamide leach liquor that obtains in the step (2) is joined the cathodic area of diaphragm sell, pH is that 0.5～1.5 acidic solution joins the positive column, be negative electrode with the titanium plate, lead-silver alloys plate is anode, is that 30～50 ℃, cathode current density are 5～50A/m at electrolyte temperature
2Electrolytic deposition 10～15h under the condition namely 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 following component by 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 the described step (1), and 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: leach in the described step (1) and be one or more snippets leaching, the copper content in the decopper(ing) anode sludge is less than 1%.
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 the 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 the 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: leach in the described step (2) and be the multistage leaching, up to the leaching yield of gold and silver respectively greater than 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) the 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: silver content is 1wt% in lead in the described step (3)-silver alloys plate.
According to claim 1 from copper anode mud the method for selective extraction gold and silver, it is characterized in that: acidic solution is the mixed solution of sulfuric acid or sulfuric acid and nitric acid in the described step (3).
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Cited By (4)
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| CN106521163A (en) * | 2016-11-05 | 2017-03-22 | 北京工业大学 | Method for copper-bearing waste chloride solution precious metal enrichment |
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