CN115449637B - Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime - Google Patents
Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime Download PDFInfo
- Publication number
- CN115449637B CN115449637B CN202211262366.7A CN202211262366A CN115449637B CN 115449637 B CN115449637 B CN 115449637B CN 202211262366 A CN202211262366 A CN 202211262366A CN 115449637 B CN115449637 B CN 115449637B
- Authority
- CN
- China
- Prior art keywords
- copper
- tellurium
- leaching
- anode slime
- selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000010949 copper Substances 0.000 title claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 106
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 44
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 38
- 239000011669 selenium Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 67
- 239000002893 slag Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 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
- 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
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0017—Sulfating or sulfiding roasting
-
- 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
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/0082—Leaching or slurrying with water
-
- 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
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
Landscapes
- 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)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime, which comprises the following steps: step one, roasting O 2-SO2 to separate selenium to obtain calcine and selenium enriched material; step two, leaching the calcine with water or acid to separate copper to obtain copper-separated slag and copper-rich sulfate solution, and drying the copper-separated slag in an oven; and thirdly, performing alkaline leaching on the copper-separated slag to obtain tellurium-separated slag and a solution containing sodium tellurite, and drying the tellurium-separated slag in an oven for subsequent recovery of gold and silver. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from the copper anode slime provided by the embodiment of the invention has the following beneficial effects: the invention realizes the efficient step extraction of the selenium, copper and tellurium in the copper anode slime by gradually separating the selenium, copper and tellurium in the copper anode slime.
Description
Technical Field
One or more embodiments of the present disclosure relate to the technical field of metal smelting, and in particular, to a method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime.
Background
Tellurium has good physical properties, is an indispensable key material for manufacturing photoelectric, semiconductor, refrigeration and other elements, and is widely applied to the high-tech fields of aerospace, military, electric and the like. Tellurium is often accompanied in minerals such as copper, lead, nickel and the like, and according to statistics, tellurium is mainly derived from copper anode slime and lead anode slime, and about 90% of tellurium is produced in the copper anode slime worldwide, so that the efficient extraction of tellurium from the copper anode slime is significant. Copper anode slime is composed of various substances of anode copper which are insoluble in electrolyte in the electrolytic refining process, and generally contains Au, ag, cu, pb, se, te, sn, as and other elements. At present, a series of researches on tellurium extraction from copper anode slime have been carried out at home and abroad, and mainly comprise a sulfating roasting-alkaline leaching method, an oxidizing roasting-sulfuric acid leaching method, a soda roasting-sulfuric acid leaching method, a tellurium chloride extraction method, an acidic oxidation leaching method, a pressurized alkaline leaching method and the like. Currently, the sulfatizing roasting method is a common process for treating copper anode slime, and about half of copper anode slime in the world is treated by the method. It is reported that the tellurium leaching rate is low and the comprehensive recovery rate is less than 60% in the tellurium separating process of the copper anode slime of the current copper smelting enterprises. Researchers have developed a lot of work against the problem of low leaching rate of alkaline leaching tellurium, mainly put forward methods such as mixed acid leaching, pressurized high alkaline leaching, acid oxidation leaching, external field strengthening, etc. Chinese patent CN111606308A discloses a method for efficiently separating copper sludge from copper slag and recovering tellurium, which adopts a hydrochloric acid oxidation system to realize the efficient leaching process of tellurium by the copper sludge from copper slag, and the tellurium leaching rate is more than 90%. Chinese patent CN110550611A discloses a method for efficiently leaching tellurium from copper-separating slag of copper anode slime by external field action reinforcement, under the external field reinforcement action of ultrasonic wave-microwave cooperation, sodium hydroxide is used as a leaching agent, sodium chlorate is used as an oxidant to leach the copper-separating slag, so that the efficient leaching of tellurium at normal pressure is realized, and the tellurium leaching rate is improved by 26-35%. Although the method can improve the tellurium leaching rate to a certain extent, the method has the problems of long process flow, high equipment requirement and high production cost, and is difficult to industrially popularize and apply.
In summary, the present application provides a method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime, which solves the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the problems in the background art, and one or more embodiments of the present specification aim to provide a method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime, which has low production cost and good economic benefit.
In view of the above, one or more embodiments of the present disclosure provide a method for efficiently separating and extracting selenium, copper, and tellurium from copper anode slime in steps, including the following steps:
step one, roasting O 2-SO2 to separate selenium: drying, crushing and grinding copper anode slime, sieving with a 100-200 mesh sieve for later use, adding a proper amount of copper anode slime into a corundum crucible, placing the corundum crucible in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, heating the atmosphere furnace, roasting and preserving heat to obtain roasted sand and selenium enriched matters after selenium steaming;
step two, leaching the calcine with water or acid to separate copper: leaching or acid leaching the calcine obtained in the step one to separate copper to obtain a copper-rich sulfuric acid solution and copper-separated slag: grinding the calcine, sieving with a 100-200 mesh sieve for later use, adding a proper amount of the calcine into a conical flask, adding a certain amount of deionized water or sulfuric acid, leaching for a period of time in a water bath at a certain temperature, filtering, separating solid from liquid to obtain copper-separated slag and copper-enriched sulfate solution, and drying the copper-separated slag in an oven;
Step three, separating copper slag and alkaline leaching tellurium: grinding the copper-separated slag obtained in the second step to a certain granularity for later use, adding a proper amount of copper-separated slag into a conical flask, adding NaOH solution, leaching for a period of time in a water bath at a certain temperature, filtering, carrying out solid-liquid separation to obtain tellurium-separated slag and sodium tellurite-containing solution, and drying the tellurium-separated slag in an oven for subsequent recovery of gold and silver.
Preferably, the flow ratio of the O 2:SO2 to the water in the first step is 2:8-10:0, the roasting temperature is 300-1000 ℃, and the roasting time is 0.5-5 h.
Preferably, the copper anode slime in the first step is derived from the composition of various substances of anode copper insoluble in electrolyte in the electrolytic refining process, contains one or more element combinations of Au, ag, cu, pb, se, te, S and As, and can also be copper anode slime after removing arsenic, antimony and bismuth or materials containing copper telluride, wherein the copper anode slime comprises the following elements in percentage by mass of Cu (5-40%), te (0.5-10%), se (0.5-10%), pb (1-10%) and Ag (2-15%).
Preferably, the O 2、SO2 gas in the first step is a pure gas or a mixed gas filled with an inert gas.
Preferably, the leaching condition of the second step is that the leaching temperature is 25-95 ℃, the stirring speed is 300-500 r/min, the liquid-solid ratio is 1-8:1, the leaching reaction time is 0.5-5 h, and the condition of acid leaching and copper separation in the second step is that the sulfuric acid concentration is 0-400 g/L.
Preferably, the alkaline leaching condition in the step three is that the concentration of NaOH solution is 50-400 g/L, the leaching temperature is 25-95 ℃, the liquid-solid ratio is 1-8:1, and the leaching time is 0.5-5 h.
According to the above, the method for efficiently and stepwise separating and extracting selenium, copper and tellurium from the copper anode slime provided by the embodiment of the invention has the following beneficial effects: according to the invention, selenium, copper and tellurium in the copper anode slime are gradually separated, so that the efficient step extraction of the selenium, copper and tellurium in the copper anode slime is realized; meanwhile, O 2 used in roasting can be obtained through compressed air, SO 2 is a byproduct obtained after copper smelting flue gas purification, SO that the production cost of the method is low, and the effects of high-efficiency cascade recycling and economy of comprehensive treatment of copper anode slime are achieved.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a process flow diagram of the present invention
FIG. 2 is a graph showing the relationship between O 2-SO2 and the selenium and tellurium leaching rates according to the present invention;
FIG. 3 shows the XRD patterns of the product of the copper anode slime O 2-SO2 of the present invention after calcination.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples.
The copper anode slime used in the embodiment of the invention comprises the following chemical components: cu (20.22%), pb (8.36%), se (6.64%), S (6.69%), ag (4.89%), te (2.87%), sn (4.26%), ba (4.01%), as (4.34%).
Example 1
Step one: grinding 20.0g of dried copper anode slime raw material to 200 mesh sieve, adding copper anode slime into a corundum crucible, placing in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, controlling the flow ratio of O 2:SO2 to be 5:5, then heating the atmosphere furnace to 600 ℃ at the heating rate of 10 DEG/min, roasting and preserving heat for 2 hours to obtain copper anode slime calcine and selenium enriched matters.
Step two: grinding 15.0g of the calcine obtained in the step one to pass through a 200-mesh sieve, adding the ground calcine into a conical flask, adding a certain amount of deionized water, controlling the liquid-solid ratio to be 1:4, leaching in a water bath kettle with the stirring rate of 400r/min and the temperature of 85 ℃ for 3 hours, filtering, and separating solid from liquid to obtain copper-separated slag and copper-rich sulfate solution.
Step three: grinding 5.0g of the dried copper-separated slag obtained in the second step to 200 meshes, adding the ground copper-separated slag into a NaOH solution with the concentration of 100g/L, controlling the liquid-solid ratio to be 4:1, leaching the copper-separated slag in a water bath kettle with the stirring rate of 400r/min and the temperature of 85 ℃ for 3 hours, filtering the leached copper-separated slag, and separating solid from liquid to obtain tellurium-separated slag and sodium tellurite-rich solution. The volatilization rate of selenium is 98.22%, the leaching rate of copper is 92.16%, and the leaching rate of tellurium is 73.11%.
Example 2
Step one: grinding 20.0g of dried copper anode slime raw material to 200 mesh sieve, adding copper anode slime into a corundum crucible, placing in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, controlling the flow ratio of O 2:SO2 to be 6:4, then heating the atmosphere furnace to 600 ℃ at the heating rate of 10 DEG/min, roasting and preserving heat for 2 hours to obtain copper anode slime calcine and selenium enriched matters.
Step two: grinding 15.0g of the calcine obtained in the step one to pass through a 200-mesh sieve, adding the ground calcine into a conical flask, adding a certain amount of deionized water to control the liquid-solid ratio to be 1:4, leaching in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering, and separating solid from liquid to obtain copper-separated slag and copper-rich sulfate solution.
Step three: grinding 5.0g of the dried copper-separated slag obtained in the second step to 200 meshes, adding the ground copper-separated slag into a NaOH solution with the concentration of 100g/L, controlling the liquid-solid ratio to be 4:1, leaching the copper-separated slag in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering the leached liquid, and separating solid from liquid to obtain tellurium-separated slag and sodium tellurite-rich solution. The volatilization rate of selenium is 98.16%, the leaching rate of copper is 91.35%, and the leaching rate of tellurium is 75.18%.
Example 3
Step one: grinding 20.0g of dried copper anode slime raw material to 200 mesh sieve, adding copper anode slime into a corundum crucible, placing in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, controlling the flow ratio of O 2:SO2 to be 7:3, then heating the atmosphere furnace to 600 ℃ at the heating rate of 10 DEG/min, roasting and preserving heat for 3 hours to obtain copper anode slime calcine and selenium enriched matters.
Step two: grinding 15.0g of the calcine obtained in the step one to pass through a 200-mesh sieve, adding the ground calcine into a conical flask, adding a certain amount of deionized water to control the liquid-solid ratio to be 1:4, leaching in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering, and separating solid from liquid to obtain copper-separated slag and copper-rich sulfate solution.
Step three: grinding 5.0g of the dried copper-separated slag obtained in the second step to 200 meshes, adding the ground copper-separated slag into a NaOH solution with the concentration of 100g/L, controlling the liquid-solid ratio to be 4:1, leaching the copper-separated slag in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering the leached liquid, and separating solid from liquid to obtain tellurium-separated slag and sodium tellurite-rich solution. The volatilization rate of selenium is 98.46%, the leaching rate of copper is 90.59%, and the leaching rate of tellurium is 83.27%.
Example 4
Step one: grinding 20.0g of dried copper anode slime raw material to 200 mesh sieve, adding copper anode slime into a corundum crucible, placing in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, controlling the flow ratio of O 2:SO2 to be 8:2, then heating the atmosphere furnace to 600 ℃ at the heating rate of 10 DEG/min, roasting and preserving heat for 2 hours to obtain copper anode slime calcine and selenium enriched matters.
Step two: grinding 15.0g of the calcine obtained in the step one to pass through a 200-mesh sieve, adding the ground calcine into a conical flask, adding a certain amount of deionized water to control the liquid-solid ratio to be 1:4, leaching in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering, and separating solid from liquid to obtain copper-separated slag and copper-rich sulfate solution.
Step three: grinding 5.0g of the dried copper-separated slag obtained in the first step to 200 meshes, adding the ground copper-separated slag into a NaOH solution with the concentration of 100g/L, controlling the liquid-solid ratio to be 4:1, leaching the copper-separated slag in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering the leached liquid-separated slag, and separating solid from liquid to obtain tellurium-separated slag and sodium tellurite-rich solution. The volatility of selenium is 93.54%, the leaching rate of copper is 88.92%, and the leaching rate of tellurium is 75.07%.
Example 5:
Step one: grinding 20.0g of dried copper anode slime raw material to 200 mesh sieve, adding copper anode slime into a corundum crucible, placing in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, controlling the flow ratio of O 2:SO2 to be 7:3, then heating the atmosphere furnace to 650 ℃ at the heating rate of 10 DEG/min, roasting and preserving heat for 3 hours to obtain copper anode slime calcine and selenium enriched matters.
Step two: grinding 15.0g of the calcine obtained in the step one to pass through a 200-mesh sieve, adding the ground calcine into a conical flask, adding a certain amount of deionized water to control the liquid-solid ratio to be 1:4, leaching in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering, and separating solid from liquid to obtain copper-separated slag and copper-rich sulfate solution.
Step three: grinding 5.0g of the dried copper-separated slag obtained in the second step to 200 meshes, adding the ground copper-separated slag into a NaOH solution with the concentration of 100g/L, controlling the liquid-solid ratio to be 4:1, leaching the copper-separated slag in a water bath kettle at the temperature of 85 ℃ for 3 hours, filtering the leached liquid, and separating solid from liquid to obtain tellurium-separated slag and sodium tellurite-rich solution. The volatilization rate of selenium is 98.23%, the leaching rate of copper is 86.74%, and the leaching rate of tellurium is 82.09%.
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (6)
1. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime is characterized by comprising the following steps of:
step one, roasting O 2-SO2 to separate selenium: drying, crushing and grinding copper anode slime, sieving with a 100-200 mesh sieve for later use, adding a proper amount of copper anode slime into a corundum crucible, placing the corundum crucible in an atmosphere furnace, simultaneously introducing O 2、SO2 gas into the atmosphere furnace, heating the atmosphere furnace, roasting and preserving heat to obtain roasted sand and selenium enriched matters after selenium steaming;
step two, leaching the calcine with water or acid to separate copper: leaching or acid leaching the calcine obtained in the step one to separate copper to obtain a copper-rich sulfuric acid solution and copper-separated slag: grinding the calcine, sieving with a 100-200 mesh sieve for later use, adding a proper amount of the calcine into a conical flask, adding a certain amount of deionized water or sulfuric acid, leaching for a period of time in a water bath at a certain temperature, filtering, separating solid from liquid to obtain copper-separated slag and copper-enriched sulfate solution, and drying the copper-separated slag in an oven;
Step three, separating copper slag and alkaline leaching tellurium: grinding the copper-separated slag obtained in the second step to a certain granularity for later use, adding a proper amount of copper-separated slag into a conical flask, adding NaOH solution, leaching for a period of time in a water bath at a certain temperature, filtering, carrying out solid-liquid separation to obtain tellurium-separated slag and sodium tellurite-containing solution, and drying the tellurium-separated slag in an oven for subsequent recovery of gold and silver.
2. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime according to claim 1, wherein the flow ratio of the introduced O 2:SO2 in the first step is 5:5-8:2, the roasting temperature is 200-1000 ℃, and the roasting time is 0.5-5 h.
3. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime according to claim 1, wherein the copper anode slime in the first step is derived from the composition of various substances of anode copper insoluble in electrolyte in the electrolytic refining process, and contains one or more element combinations of Au, ag, cu, pb, se, te, S and As, and the copper anode slime contains Cu (5-40%), te (0.5-10%), se (0.5-10%), pb (1-10%) and Ag (2-15%) in percentage by mass.
4. The method for efficiently separating and extracting selenium, copper and tellurium from copper anode slime in a step-wise manner according to claim 1, wherein the O 2、SO2 gas in the first step is pure gas or mixed gas filled with inert gas.
5. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime according to claim 1, wherein the leaching condition of the second step is that the leaching temperature is 25-95 ℃, the stirring speed is 300-500 r/min, the liquid-solid ratio is 1-8:1, the leaching reaction time is 0.5-5 h, and the condition of acid leaching and copper separating in the second step is that the sulfuric acid concentration is 0-400 g/L.
6. The method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime according to claim 1, wherein the alkaline leaching condition in the step three is that the concentration of NaOH solution is 50-400 g/L, the leaching temperature is 25-95 ℃, the liquid-solid ratio is 1-8:1, and the leaching time is 0.5-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262366.7A CN115449637B (en) | 2022-10-14 | 2022-10-14 | Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262366.7A CN115449637B (en) | 2022-10-14 | 2022-10-14 | Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115449637A CN115449637A (en) | 2022-12-09 |
| CN115449637B true CN115449637B (en) | 2024-04-19 |
Family
ID=84310088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211262366.7A Active CN115449637B (en) | 2022-10-14 | 2022-10-14 | Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115449637B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745657A (en) * | 2012-07-30 | 2012-10-24 | 阳谷祥光铜业有限公司 | Method for extracting tellurium from tellurium copper slags |
| CN107574300A (en) * | 2017-08-29 | 2018-01-12 | 山东恒邦冶炼股份有限公司 | A kind of mixed processing technique of copper, lead anode slurry |
| CN112695200A (en) * | 2020-12-22 | 2021-04-23 | 万载志成实业有限公司 | Method for recovering selenium, gold and silver from copper anode slime |
| US11408051B2 (en) * | 2017-03-30 | 2022-08-09 | Dundee Sustainable Technologies Inc. | Method and system for metal recovery from arsenical bearing sulfides ores |
-
2022
- 2022-10-14 CN CN202211262366.7A patent/CN115449637B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745657A (en) * | 2012-07-30 | 2012-10-24 | 阳谷祥光铜业有限公司 | Method for extracting tellurium from tellurium copper slags |
| US11408051B2 (en) * | 2017-03-30 | 2022-08-09 | Dundee Sustainable Technologies Inc. | Method and system for metal recovery from arsenical bearing sulfides ores |
| CN107574300A (en) * | 2017-08-29 | 2018-01-12 | 山东恒邦冶炼股份有限公司 | A kind of mixed processing technique of copper, lead anode slurry |
| CN112695200A (en) * | 2020-12-22 | 2021-04-23 | 万载志成实业有限公司 | Method for recovering selenium, gold and silver from copper anode slime |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115449637A (en) | 2022-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105734299B (en) | A kind of method of oxygen pressure treatment tin anode mud comprehensively recovering valuable metal | |
| CN101565174B (en) | Method for extracting refined tellurium from tellurium-contained smelting slag | |
| CN111575483B (en) | Method for separating selenium, tellurium, arsenic, copper, lead and silver and enriching gold from copper anode slime | |
| CN105112668B (en) | Method for separating and enriching valuable metals from copper anode mud | |
| US8277772B2 (en) | Method of extracting Te and bismuth oxide and recovering byproducts | |
| CN113308606B (en) | Method for leaching and separating valuable metals from silver-gold-rich selenium steaming slag | |
| CN102392141B (en) | Method for separating tellurium from precious metals | |
| CN107460324A (en) | A kind of method that silver anode slime control current potential prepares four or nine gold medals | |
| CN107557589B (en) | A method of recycling valuable metal from zinc hydrometallurgy copper-cadmium slag | |
| CN107447105A (en) | A kind of method that copper anode mud control current potential separates and is enriched with tellurium | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN105063361B (en) | Method for comprehensively recovering valuable metal from copper anode slime | |
| CN108359805A (en) | A kind of method of Whote-wet method processing tin copper ashes | |
| WO2023061389A1 (en) | Recovery method for valuable metal in copper anode mud | |
| CN104911366A (en) | Method for recovering valuable metals from silver-bismuth slag through using aqua regia | |
| CN112063850A (en) | Method for recovering valuable metals after alkaline leaching and dehalogenation of circuit board smelting smoke dust | |
| CN105886785A (en) | Method for preparing high-purity silver powder from silver-rich residue containing high selenium and tellurium | |
| CN112063854A (en) | Method for comprehensively recovering bismuth, silver and copper metals by taking precious lead as raw material | |
| CN109207733B (en) | Preparation method for extracting tellurium from tellurium copper slag | |
| CN115449637B (en) | Method for efficiently and stepwise separating and extracting selenium, copper and tellurium from copper anode slime | |
| CN105983707B (en) | A method of high-purity rhenium powder is prepared from rhenium-containing high arsenic-and copper-bearing sulfide | |
| CN113337724B (en) | Method for synchronously separating and extracting rare-dispersion element tellurium and metal copper from cuprous telluride slag | |
| CN104498724B (en) | A kind of remove dilute noble alloy blowing slag in lead, arsenic, antimony, the method for bismuth | |
| CN111748828A (en) | Method for recycling copper, silver, selenium and tellurium through molten salt electrolysis of copper anode slime | |
| CN111268655B (en) | Method for producing tellurium dioxide by self-purifying crude tellurium powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |