CN109371228A - A method of recycling selenium, tellurium, copper and noble metal from copper anode mud - Google Patents
A method of recycling selenium, tellurium, copper and noble metal from copper anode mud Download PDFInfo
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- CN109371228A CN109371228A CN201811353615.7A CN201811353615A CN109371228A CN 109371228 A CN109371228 A CN 109371228A CN 201811353615 A CN201811353615 A CN 201811353615A CN 109371228 A CN109371228 A CN 109371228A
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- copper
- tellurium
- selenium
- lead
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000010949 copper Substances 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 50
- 239000011669 selenium Substances 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 31
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 9
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 22
- 239000010970 precious metal Substances 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006256 anode slurry Substances 0.000 claims abstract description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 15
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 14
- 230000001180 sulfating effect Effects 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- QZCHKAUWIRYEGK-UHFFFAOYSA-N tellanylidenecopper Chemical compound [Te]=[Cu] QZCHKAUWIRYEGK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 230000000717 retained effect Effects 0.000 claims abstract description 3
- 239000003500 flue dust Substances 0.000 claims description 15
- 239000003610 charcoal Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910001152 Bi alloy Inorganic materials 0.000 abstract description 10
- 229910000967 As alloy Inorganic materials 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- 229910018162 SeO2 Inorganic materials 0.000 abstract description 4
- -1 antimony gold copper arsenic Chemical compound 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract 1
- 230000001698 pyrogenic effect Effects 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910003597 H2SeO3 Inorganic materials 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910018030 Cu2Te Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- SMLWXDQNMGBSBD-UHFFFAOYSA-N [Cu].[Sb].[As].[Ag] Chemical compound [Cu].[Sb].[As].[Ag] SMLWXDQNMGBSBD-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001447 alkali salts Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a kind of method that selenium, tellurium, copper and noble metal are recycled from copper anode mud, carries out segment processing to copper anode mud, first carries out sulfating roasting to copper anode mud, obtain SeO2、SO2、SO3Deng mixed gas and calcining, mixed gas will be obtained absorb reduction being dried to obtain impure selenium, then impure selenium is put into vacuum distillation furnace, purification obtains smart selenium；The calcining that sulfating roasting is obtained carries out oxygen pressure acidleach, to obtain the lead anode slurry of cupric, the leachate of tellurium and deselenization, copper, tellurium；Copper powder reduction treatment is carried out to the leachate of cupric, tellurium, copper tellurium slag and copper-bath are obtained after reaction, so as to the recycling to copper and tellurium；The lead anode slurry of deselenization, copper is subjected to reduction melting, obtain precious metals containing lead alloy, precious metals containing lead alloy is put into continuous vacuum retort, volatile lead, bismuth is set to enter volatilization phase, to recycle high-grade lead, and the metal of the difficult volatilization such as gold, silver, copper, antimony, arsenic is retained in residue, alloy is formed, convenient for the recycling of subsequent noble metal.Method provided by the invention can obtain the smart selenium that purity is 99.9 ~ 99.99%, copper-bath, copper tellurium slag, lead bismuth alloy, silver-colored antimony gold copper arsenic alloy.
Description
Technical field
The method that the present invention relates to a kind of to recycle selenium, tellurium, copper and noble metal from copper anode mud belongs to copper anode mud processing
Technical field.
Technical background
Copper anode mud is the smelting byproducts generated in electrolytic refining course of copper, and each component is mostly with metal, sulfide, selen-tellurjum
Compound, oxide, elemental sulfur and complicated basic salt form exist.It is the important source material of cupper smelting synthetical recovery, right
The economic benefit of enterprise has a very big impact.Copper anode mud is rich in rare gold such as noble metals and selenium, tellurium such as Au Ag Pt Pds
Belong to, the base metals such as Yi Jitong, lead.
Tradition copper anode slime treatment process mainly has three categories both at home and abroad: first is that traditional thermal process process；Second is that half
Wet processing process；Third is that Whote-wet method treatment process.(1) traditional firing method process, that is, pyrogenic process-electrolysis process of copper anode mud processing
Process is the copper anode slime treatment process that pyrogenic process and wet process combine based on pyrogenic process.Its technical process includes: acidleach
Decopper(ing), precious metals containing lead furnace reduction smelting, dividing silver stove refinement oxide, gold and silver electrorefining etc., (2) half wet process treatment process is to be with wet process
The process flow that master, pyrogenic process and wet process combine mainly has low-temperature oxidation roasting-wet processing process, pressure leaching process, lives
Friendly method technique, using abstraction technique extraction of gold process etc..Most of half wet process technique all remains pyrogenic process roasting recycling selenium, and restores
The firing method process such as melting, refinement oxide are then changed to wet-treating.(3) Whote-wet method treatment process: Whote-wet method treatment process is using dilute
Sulfuric acid, air or oxygen Oxidation Leaching decopper(ing), then selected with chlorine, sodium chlorate or hydrogen peroxide as oxidant control leaching process current potential
Selecting property, which leaches, shines.Then ammonium hydroxide or sodium sulfite Leaching of Silver are used, reduction obtains silver powder.It is finally golden with sodium chlorate or chlorine leaching,
Leachate oxalic acid restores to obtain bronze, and thick gold, silver powder is electrolysed to obtain pure metal.
Conventional process techniques are mature, be easy to control, processing capacity is big, but there are long flow path, metal recovery rate is low, energy consumption
The problems such as height, pollution big, at high cost.Compared with traditional handicraft, the present invention can shorten the process flow of precious metals containing lead processing, improve gold
Silver raising recovery rate reduces and smelts production energy consumption；Meanwhile vacuum distillation process is simple, generates without waste water and gas, it is environmental-friendly, and at
This is lower.
Summary of the invention
The present invention provides a kind of to efficiently separate the new side of cleaning of recycling selenium, tellurium, copper and noble metal from copper anode mud mud
Method, the present invention are achieved through the following technical solutions:
(1) copper anode mud is subjected in rotary kiln sulfating roasting and obtains flue dust containing selenium and calcining, the obtained warp of flue dust containing selenium
Water is crossed to absorb, restore, obtain the impure selenium (SeO in flue dust after drying2It is only absorbed by the water as H2SeO3Solution, and then by flue dust
SO2Gas reduction is 90%~99% at elemental selenium, the purity of impure selenium), impure selenium is purified to obtain smart selenium using vacuum distillation method；
(2) calcining for obtaining sulfating roasting carries out oxygen pressure acidleach, obtains the leaching of cupric, the leachate of tellurium and decopper(ing), selenium, tellurium
It slags tap-lead anode slurry；Cupric, tellurium leachate in excessive copper powder be added carry out reduction treatment, obtain copper tellurium slag and sulfuric acid
Copper solution, and then can synthetical recovery metal copper and tellurium.
(3) lead anode slurry supplying charcoal is subjected to reduction melting, obtains precious metals containing lead alloy, wherein reduction temperature is 800 ~ 1200
℃；
(4) precious metals containing lead alloy was subjected to vacuum distillation, volatile lead, bismuth enter volatilization phase, and the metal of hardly possible volatilization is retained in residual
It stays in object, forms alloy.
Preferably, in step (1) of the present invention sulfating roasting detailed process are as follows: copper anode mud and the concentrated sulfuric acid (quality hundred
Divide specific concentration for 98%) feeder of the earth of positive pole through feeder trough in ratio pulp in stirred tank that quality is 1:1, after pulp
It is equably sent into rotary kiln, maturing temperature is 500~550 DEG C, and the time is 1 ~ 4h.
Preferably, the condition that vacuum distillation method purifies in step (1) of the present invention are as follows: the heating method of vacuum drying oven is to add indirectly
Heat, the fire box temperature of vacuum drying oven are 200~450 DEG C, and vacuum degree is 1~100Pa.
Preferably, calcining carries out the condition that oxygen presses acidleach in step (2) of the present invention are as follows: and acidity 100g/L, temperature 100 ~
150 DEG C, 30 ~ 60min of extraction time, leach 0.8 Mpa of pressure, liquid-solid ratio 5:1, under this condition decopper(ing) rate up to 98% with
On, Copper in Slag is less than 0.3%.
Preferably, the mass ratio of charcoal and lead anode slurry is (0.1~1) in step (3) of the present invention: 1.
Preferably, the process being evaporated in vacuo in step (4) of the present invention are as follows: precious metals containing lead alloy is put into continuous vacuum furnace,
Under the conditions of 1 ~ 100Pa pressure and 900~1200 DEG C of vapo(u)rizing temperature, volatile lead, bismuth enter volatilization phase, and condensation is pooled to
Catch tray；Gold, silver, copper, antimony, the arsenic of hardly possible volatilization then stay in evaporating pan, form alloy, finally, volatile matter and residue difference
It is released from two discharge ports of continuous vacuum furnace.
The main component of copper anode mud of the present invention be Cu 10 ~ 50%, Ag 3 ~ 30%, Au 0.01 ~ 5%, Pb 5 ~
20%、Se 2~15%、Te 0.1~10%、As 0.1~5%、Sb 0.1~5%、Bi 0.1~5%、Ni 0.1~5%、SiO2 0.1~5%。
The purity of obtained impure selenium is 90%~99% in step (2) of the present invention, also contains other impurities 1 ~ 10%, impurity
Main component is Cu 0.01 ~ 1%, 1 ~ 1000g/t of Ag, 0.1 ~ 100g/t of Au, Pb 0.01 ~ 2%, Te 0.01 ~ 2%, As 0.01
~1%、Sb 0.01~1%、Bi 0.01~1%、Ni 0.01~1%。
Beneficial effects of the present invention: copper anode slime treatment process provided by the invention can obtain the higher smart selenium of purity, enrichment
The copper tellurium slag of tellurium can be used for recycling the copper-bath of copper and the alloy of tractable lead bismuth alloy and gold and silver copper-stibium-arsenic.Lead
Bismuth alloy returns to lead smelting technology and lead and bismuth is separately recovered, and gold, silver and bronze antimony arsenic alloy can directly return to point silver stove and carry out refinement oxide
Dearsenification antimony and noble metal recycling.
Vacuum distillation method provided by the invention can not only obtain the smart selenium that purity is 99.9% ~ 99.99%, be easily isolated
Lead, bismuth alloy and gold, silver, copper, antimony, arsenic alloy, and copper and enrichment tellurium can be recycled, and process is simple, produces without waste water and gas
It is raw, it is environmental-friendly, and cost is lower.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
(1) copper anode mud sulfating roasting is carried out to obtain containing SeO in rotary kiln2Flue dust and calcining, copper anode mud and sulphur
Sour (98%) is ratio pulp in stirred tank of 1:1 in mass ratio, and feeder is equably in feeder trough for the earth of positive pole after pulp
It is sent into rotary kiln, carries out roasting operation, maturing temperature is 500 DEG C, time 4h, and what is obtained contains SeO2Flue dust by water absorb
For H2SeO3Solution, and then by the SO in flue dust2Gas reduction at elemental selenium, obtained after dry impure selenium (purity of selenium is 90%~
99%), by impure selenium use vacuum distillation method purify to obtain smart selenium (heating method of vacuum drying oven for indirect heating, the burner hearth of vacuum drying oven
Temperature is 400 DEG C, vacuum degree 100Pa, distillation time 2h) smart selenium is obtained, essence is detected according to professional standard YS/T223-2007
Selenium purity, the purity of final selenium is up to 99.96%.
(2) calcining obtained sulfating roasting carry out the acidleach of oxygen pressure (condition are as follows: acidity 100g/L, 100 DEG C of temperature,
Extraction time 30min, 0.8 Mpa of pressure, liquid-solid ratio 5:1 are leached), obtain cupric, the leachate of tellurium and decopper(ing), selenium, tellurium
Leached mud-lead anode slurry；In 80g/l ratio cupric, tellurium leachate in excessive copper powder be added carry out reduction treatment, obtain
To copper tellurium slag and copper-bath；Through chemical analysis and xrd material phase analysis, the main chemical compositions of copper tellurium slag be Cu39.21%,
Te16.76%, main object are mutually Cu2Te、Cu7Te4、Cu2-xTe etc..
(3) lead anode slurry supplying charcoal reduction is carried out in the ratio that the mass ratio of charcoal and lead anode slurry is 0.1:1 to melt
It refines (pyrogenic process), obtains precious metals containing lead alloy, wherein reduction temperature is 800 DEG C, time 3h；
(4) precious metals containing lead alloy was subjected to vacuum distillation, precious metals containing lead alloy was put into continuous vacuum furnace, in 100Pa pressure and 900
DEG C vapo(u)rizing temperature under the conditions of, volatile lead, bismuth enter volatilization phase, and condensation is pooled to catch tray；Hardly possible volatilization gold, silver, copper,
Antimony, arsenic then stay in evaporating pan, form alloy, finally, volatile matter and residue are respectively from two dischargings of continuous vacuum furnace
Mouth is released.
Respectively obtain Pb-Bi alloy and Ag-Au-Cu-Sb-As alloy.Ag content is 19g/t in volatile matter Pb-Bi alloy,
Au content is less than 0.1g/t.Wherein, lead, bismuth removal efficiency be respectively 97.87% and 98.76%, silver, gold direct yield reach respectively
99.68% and 99.91%.
Embodiment 2
(1) copper anode mud sulfating roasting is carried out to obtain containing SeO in rotary kiln2Flue dust and calcining, copper anode mud and sulphur
Sour (98%) is ratio pulp in stirred tank of 1:1 in mass ratio, and feeder is equably in feeder trough for the earth of positive pole after pulp
It is sent into rotary kiln, carries out roasting operation, maturing temperature is 520 DEG C, time 3h, and what is obtained contains SeO2Flue dust by water absorb
For H2SeO3, and then by the SO in flue dust2Gas reduction obtains impure selenium (90%~99%) after dry, impure selenium is used at elemental selenium
(heating method of vacuum drying oven is indirect heating, and the fire box temperature of vacuum drying oven is 310 DEG C, and vacuum degree is for vacuum distillation method purification
30Pa, distillation time 1.5h) smart selenium is obtained, smart selenium purity, the purity of final selenium are detected according to professional standard YS/T223-2007
Up to 99.97%.
(2) calcining obtained sulfating roasting carry out the acidleach of oxygen pressure (condition are as follows: acidity 100g/L, 150 DEG C of temperature,
Extraction time 50min, 0.8 Mpa of pressure, liquid-solid ratio 5:1 are leached), obtain cupric, the leachate of tellurium and decopper(ing), selenium, tellurium
Leached mud-lead anode slurry；In 40g/l ratio cupric, tellurium leachate in excessive copper powder be added carry out reduction treatment, obtain
To copper tellurium slag and copper-bath；Through chemical analysis and xrd material phase analysis, the main chemical compositions of copper tellurium slag be Cu36.34%,
Te19.54%, main object are mutually Cu2Te、Cu7Te4、Cu2-xTe etc..
(3) lead anode slurry is incorporated charcoal in the ratio that the mass ratio of charcoal and lead anode slurry is 1:1 and carries out reduction melting
(pyrogenic process) obtains precious metals containing lead alloy, and wherein reduction temperature is 1200 DEG C, time 1.5h；
(4) precious metals containing lead alloy was subjected to vacuum distillation, precious metals containing lead alloy was put into continuous vacuum furnace, in 50Pa pressure and 1000
DEG C vapo(u)rizing temperature under the conditions of, volatile lead, bismuth enter volatilization phase, and condensation is pooled to catch tray；Hardly possible volatilization gold, silver, copper,
Antimony, arsenic then stay in evaporating pan, form alloy, finally, volatile matter and residue are respectively from two dischargings of continuous vacuum furnace
Mouth is released.
Respectively obtain Pb-Bi alloy and Ag-Au-Cu-Sb-As alloy.Ag content is 19g/t in volatile matter Pb-Bi alloy,
Au content is less than 0.1g/t.Wherein, lead, bismuth removal efficiency be respectively 97.87% and 98.76%, silver, gold direct yield reach respectively
99.68% and 99.91%.
Embodiment 3
(1) copper anode mud sulfating roasting is carried out to obtain containing SeO in rotary kiln2Flue dust and calcining, copper anode mud and sulphur
Sour (98%) is ratio pulp in stirred tank of 1:1 in mass ratio, and feeder is equably in feeder trough for the earth of positive pole after pulp
It is sent into rotary kiln, carries out roasting operation, maturing temperature is 550 DEG C, time 2.5h, and what is obtained contains SeO2Flue dust by water inhale
Receiving is H2SeO3Solution, and then by the SO in flue dust2Gas reduction obtains impure selenium (90%~99%) after dry at elemental selenium, will be thick
Selenium uses vacuum distillation method to purify to obtain smart selenium, and (for the heating method of vacuum drying oven for indirect heating, the fire box temperature of vacuum drying oven is 240
DEG C, vacuum degree 10Pa, distillation time 1h) smart selenium is obtained, smart selenium purity is detected according to professional standard YS/T223-2007, finally
The purity of selenium is up to 99.93%.
(2) calcining obtained sulfating roasting carry out the acidleach of oxygen pressure (condition are as follows: acidity 100g/L, 125 DEG C of temperature,
Extraction time 60min, 0.8 Mpa of pressure, liquid-solid ratio 5:1 are leached), obtain cupric, the leachate of tellurium and decopper(ing), selenium, tellurium
Leached mud-lead anode slurry；In 20g/l ratio cupric, tellurium leachate in excessive copper powder be added carry out reduction treatment, obtain
To copper tellurium slag and copper-bath；Through chemical analysis and xrd material phase analysis, the main chemical compositions of copper tellurium slag be Cu31.98%,
Te20.76%, main object are mutually Cu2Te、Cu7Te4、Cu2-xTe etc..
(3) lead anode slurry supplying charcoal reduction is carried out in the ratio that the mass ratio of charcoal and lead anode slurry is 0.5:1 to melt
It refines (pyrogenic process), obtains precious metals containing lead alloy, wherein reduction temperature is 1000 DEG C, time 2h；
(4) precious metals containing lead alloy was subjected to vacuum distillation, precious metals containing lead alloy was put into continuous vacuum furnace, in 1Pa pressure and 1200
DEG C vapo(u)rizing temperature under the conditions of, volatile lead, bismuth enter volatilization phase, and condensation is pooled to catch tray；Hardly possible volatilization gold, silver, copper,
Antimony, arsenic then stay in evaporating pan, form alloy, finally, volatile matter and residue are respectively from two dischargings of continuous vacuum furnace
Mouth is released.
Respectively obtain Pb-Bi alloy and Ag-Au-Cu-Sb-As alloy.Ag content is 19g/t in volatile matter Pb-Bi alloy,
Au content is less than 0.1g/t.Wherein, lead, bismuth removal efficiency be respectively 97.87% and 98.76%, silver, gold direct yield reach respectively
99.68% and 99.91%.
Claims (6)
1. a kind of method for recycling selenium, tellurium, copper and noble metal from copper anode mud, which is characterized in that specifically includes the following steps:
(1) copper anode mud is subjected in rotary kiln sulfating roasting and obtains flue dust containing selenium and calcining, the obtained warp of flue dust containing selenium
It crosses water to absorb, restore, obtain impure selenium after drying, impure selenium is purified to obtain smart selenium using vacuum distillation method；
(2) calcining for obtaining sulfating roasting carries out oxygen pressure acidleach, obtains the leaching of cupric, the leachate of tellurium and decopper(ing), selenium, tellurium
It slags tap-lead anode slurry；Cupric, tellurium leachate in excessive copper powder be added carry out reduction treatment, obtain copper tellurium slag and sulfuric acid
Copper solution；
(3) lead anode slurry supplying charcoal is subjected to reduction melting, obtains precious metals containing lead alloy, wherein reduction temperature is 800 ~ 1200 DEG C；
(4) precious metals containing lead alloy was subjected to vacuum distillation, volatile lead, bismuth enter volatilization phase, and the metal of hardly possible volatilization is retained in residual
It stays in object, forms alloy.
2. method according to claim 1, it is characterised in that: the detailed process of sulfating roasting in step (1) are as follows: copper anode
Ratio pulp in stirred tank that mud and the concentrated sulfuric acid are 1:1 in quality, the earth of positive pole after pulp are uniform through the feeder of feeder trough
Rotary kiln is sent on ground, and maturing temperature is 500~550 DEG C, and the time is 1 ~ 4h.
3. method according to claim 1, it is characterised in that: the condition that vacuum distillation method purifies in step (1) are as follows: vacuum drying oven
Heating method be indirect heating, the fire box temperature of vacuum drying oven is 200~450 DEG C, and vacuum degree is 1~100Pa.
4. method according to claim 1, it is characterised in that: calcining carries out the condition of oxygen pressure acidleach in step (2) are as follows: acidity
100g/L, 100 ~ 150 DEG C of temperature, 30 ~ 60min of extraction time, 0.8 Mpa of pressure, liquid-solid ratio 5:1 are leached.
5. method according to claim 1, it is characterised in that: the mass ratio of charcoal and lead anode slurry is (0.1 in step (3)
~1): 1.
6. method according to claim 1, it is characterised in that: the process being evaporated in vacuo in step (4) are as follows: put precious metals containing lead alloy
Enter in continuous vacuum furnace, under the conditions of 1 ~ 100Pa pressure and 900~1200 DEG C of vapo(u)rizing temperature, volatile lead, bismuth enter
Volatilization phase, condensation are pooled to catch tray；Gold, silver, copper, antimony, the arsenic of hardly possible volatilization then stay in evaporating pan, form alloy.
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