CN117448587A - Combined treatment method for high-copper high-silver alloy and copper anode slime - Google Patents
Combined treatment method for high-copper high-silver alloy and copper anode slime Download PDFInfo
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- CN117448587A CN117448587A CN202311335813.1A CN202311335813A CN117448587A CN 117448587 A CN117448587 A CN 117448587A CN 202311335813 A CN202311335813 A CN 202311335813A CN 117448587 A CN117448587 A CN 117448587A
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- 239000010949 copper Substances 0.000 title claims abstract description 120
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 119
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002893 slag Substances 0.000 claims abstract description 65
- 239000011669 selenium Substances 0.000 claims abstract description 50
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 claims abstract description 42
- 238000003723 Smelting Methods 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004332 silver Substances 0.000 claims abstract description 39
- 238000007664 blowing Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 239000010931 gold Substances 0.000 claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 18
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000007781 pre-processing Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 229940091258 selenium supplement Drugs 0.000 claims description 44
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000779 smoke Substances 0.000 claims description 16
- 229910052714 tellurium Inorganic materials 0.000 claims description 13
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 10
- 229910052745 lead Inorganic materials 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- MHXARZLGBBWVEH-UHFFFAOYSA-M [O-][Se](O)(=O)=O.[Na+].[SeH2] Chemical compound [O-][Se](O)(=O)=O.[Na+].[SeH2] MHXARZLGBBWVEH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229960001881 sodium selenate Drugs 0.000 claims description 4
- 239000011655 sodium selenate Substances 0.000 claims description 4
- 235000018716 sodium selenate Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000002817 coal dust Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910018162 SeO2 Inorganic materials 0.000 claims 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 21
- 150000002739 metals Chemical class 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 239000011133 lead Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a combined treatment method of high-copper high-silver alloy and copper anode slime, which comprises the following steps: step one, preprocessing copper anode slime, carrying out filter pressing and pulp mixing and oxygen pressure acid leaching on high copper noble silver alloy and copper anode slime to obtain leaching liquid and leaching slag, and precipitating selenium in the leaching liquid: step two, reducing smelting, namely adding the leaching slag obtained in the step one into a rotary top-blowing furnace for reducing smelting; step three, oxidizing converting to obtain high-copper converting slag and gold-silver alloy; casting gold-silver alloy and SO 2 Selenium is recovered; and fifthly, treating the flue gas. The invention has the advantages that: the high copper and high silver alloy and copper anode slime are treated in a combined way, and the high copper and high silver alloy and the copper anode slime are mixed, thereby creating a copper-balancing alloyThe mixture of metal contents such as gold, silver and the like utilizes the oxidation-reduction property of metals by adopting a co-smelting and blowing process, so that valuable metals such as copper, selenium, gold, silver and the like are trapped by lead, antimony and bismuth in the materials, the purpose of effective comprehensive separation and recovery is achieved, and the cost of extraction and separation can be reduced.
Description
Technical Field
The invention relates to a combined treatment method of high-copper high-silver alloy and copper anode slime, belonging to the technical field of nonferrous metal metallurgy.
Background
The high copper and high silver alloy refers to by-products which are generated after blowing in a top-blowing furnace of lead anode slime and are rich in Cu, ag and other impurities Pb, sb, bi and other valuable metals, and the copper anode slime is a substance which is generated in the copper electrolysis process and contains Cu, noble metals (Au, ag) and other impurities (Pb, sb and Bi), and is one of important sources for recycling gold and silver.
At present, the treatment method in the production of the high-copper high-silver alloy generally directly transfers the high-copper high-silver alloy to a silver separating furnace for converting lead, bismuth and copper to produce crude silver, and the crude silver is electrolyzed to obtain silver products, but a large amount of converter slag can be produced, and then the converter slag returns to a blast furnace for reduction smelting to produce alloy and copper matte, and the copper matte is oxidized to remove lead, antimony and bismuth by converting to obtain crude copper. The production process flow is complex, the slag yield is large, and the production cost is high.
Because of single treatment of one material, partial metals cannot be recovered or the recovery rate is low due to the lower content of partial metals; the prior art has the following defects:
1. the original treatment process of the high copper and high silver alloy has low direct silver yield, copper is removed by liquation and a large amount of silver metal is taken away by impurity removal by oxidation in a silver separating furnace, the direct silver yield is affected, and the direct silver yield is only 70-80 ℃ generally. Meanwhile, the open circuit of copper is incomplete, the direct copper yield is low in the process of producing blister copper by smelting copper-removing slag and silver-separating furnace oxidizing slag treatment, and is about 50%, and half of copper metal is returned to the process, so that repeated smelting is caused.
2. The original high copper and high silver alloy process has incomplete element separation and large slag yield.
3. The cost is high, and the cost consumption is high because the high-copper high-silver alloy and the copper anode slime are treated independently.
Disclosure of Invention
The invention aims to solve the technical problem of providing a combined treatment method of high-copper high-silver alloy and copper anode slime, which mixes the high-copper high-silver alloy and the copper anode slime to create a mixture with balanced metal contents of copper, gold, silver and the like. The lead-antimony-bismuth is utilized to collect valuable metals such as copper, selenium, gold and silver, so that the valuable metals such as gold and silver can be recovered to the greatest extent, the resource waste is reduced, and meanwhile, the cost of extraction and separation can be reduced, thereby achieving the purpose of effectively and comprehensively separating and recovering the valuable metal elements.
The invention is realized by the following scheme: a combined treatment method of high copper and high silver alloy and copper anode slime comprises the following steps:
step one, preprocessing copper anode slime: crushing and uniformly mixing high-copper noble silver alloy and copper anode slime, performing filter pressing through a filter press, adding sulfuric acid and water for size mixing, then adding an oxygen autoclave for oxygen pressure acid leaching, removing part of copper and lead to obtain leaching liquid and leaching slag, introducing SO2 into the leaching liquid to precipitate selenium to obtain selenium-precipitated slag and selenium-precipitated liquid, delivering the selenium-precipitated slag to a selenium recovery process, adding copper powder into the selenium-precipitated liquid to precipitate tellurium to obtain copper telluride and tellurium-precipitated liquid, delivering the copper telluride to a tellurium recovery process, and returning the tellurium-precipitated liquid to a copper electrolysis workshop;
step two, reduction smelting: adding the leached slag obtained in the first step into a rotary top-blowing furnace, adding scrap iron, white stone and coke powder or coal dust for reduction smelting, taking silicon in the scrap iron, white stone and anode mud as a slag-forming flux to form multi-element complex melt calcium silicate slag, and after the materials are melted and fully reacted, dividing a melt formed by final smelting into two parts: the upper layer is smelting slag, and the lower layer is a precious lead alloy layer rich in Pb, sb, cu, bi, namely a precious lead alloy layer;
step three, oxidation converting: removing the upper smelting slag produced in the second step, keeping the lower noble lead alloy layer in a rotary top blowing furnace, and introducing compressed air to perform oxidation blowing to obtain high-copper blowing slag and gold-silver alloy;
step four, gold and silverAlloy casting, SO 2 And (3) recycling selenium: cleaning blowing slag floating on the surface of the melt in the third step, casting the gold-silver alloy into an anode plate to form a silver anode plate, and conveying the silver anode plate to a silver anode plate electrolysis workshop;
step five, flue gas treatment: and (3) introducing the smelting smoke from the second step and the converting smoke from the third step into a smoke treatment system to obtain selenium-rich liquid and treated smoke dust, wherein the selenium-rich liquid is sent to a selenium recovery process, and the treated smoke dust is returned to the smelting process.
In the first step, the mass ratio of the high copper noble silver alloy to the copper anode slime is 3:1-5:1.
And in the first step, the liquid-solid ratio of the size mixing is controlled to be 4/1.
The furnace temperature in the converting process in the third step is controlled to be 650-850 ℃, and the furnace temperature in the melting stage is maintained to be more than 1000 DEG C
The silver anode plate in the fourth step contains more than 96% of silver and 1-2% of gold, and the content of impurities of lead, antimony, bismuth, selenium and tellurium is controlled below 100ppm by controlling copper content to be about 1.5%.
Introducing NaOH into the flue gas in the fifth step to make SeO in the flue gas 2 Absorbing to obtain sodium selenate selenium-rich liquid, and introducing SO 2 ，SO 2 And reducing and recovering selenium in the sodium selenate to form crude selenium.
The beneficial effects of the invention are as follows:
1. according to the invention, the high-copper high-silver alloy is matched to enter a copper anode slime treatment process, so that the average content of metals such as copper, gold, silver and the like is at a higher level, the recovery rate is increased, according to the property of metal thermal reduction, pb, sb, cu, bi in the material can replace precious metals such as Se, au, ag, cu and the like, the precious metals are captured into a precious lead alloy, the content of the precious lead alloy in smelting slag is reduced, as the nonferrous metal smelting industry increasingly pays attention to the comprehensive recycling and diversified development of reinforced resources, and the combined treatment of smelting materials gradually becomes the development trend of comprehensive recycling of the valuable metals;
2. according to the invention, gold and silver rare noble metals are trapped in gold and silver alloy, copper, lead, antimony, bismuth, selenium and the like are enriched in blowing slag or smoke dust, so that the purpose of effective comprehensive separation and recovery is achieved, and the cost of extraction and separation can be reduced;
3. each operation process in the treatment process is simple and quick, the energy consumption is low, no waste water, waste and the like are generated in the whole treatment process, and the materials of the whole treatment system can be grafted to the original production process, so that the operability is high;
4. the method comprises the steps of combining high-copper high-silver alloy and copper anode slime, mixing the high-copper high-silver alloy with the copper anode slime, creating a mixture with balanced metal contents of copper, gold, silver and the like, and utilizing the oxidation-reduction property of metals by adopting a co-smelting and converting process to lead, antimony and bismuth in materials to trap valuable metals of copper, selenium, gold, silver and the like, so that the recovery efficiency of the valuable metals is improved to the greatest extent, the yield of waste residues is reduced, the waste of resources is reduced, and the method has remarkable environmental protection benefits;
5. the invention eliminates the high cost caused by separately treating the high-copper high-silver alloy and the copper-copper anode slime, and enriches the elements such as copper, lead, antimony, bismuth, selenium and the like into the blowing slag or the smoke dust by capturing the rare noble metals of gold and silver into the gold and silver alloy, thereby realizing effective comprehensive separation and recovery, and reducing the cost of the extraction and separation processes.
Drawings
FIG. 1 is a schematic flow chart of a combined treatment method of a high copper high silver alloy and copper anode slime.
Detailed Description
The invention is further described with reference to fig. 1, but the scope of the invention is not limited to this.
In the embodiment, the high copper noble silver alloy and the copper anode slime are treated in a combined way, wherein the content of each element in the high copper noble silver alloy and the copper anode slime to be treated is shown in the table 1,
TABLE 1 elemental content of high copper noble silver alloy and copper anode slime to be treated
For the combined treatment process of the high-copper noble silver alloy and the copper anode slime, the specific steps are as follows:
step one, preprocessing high copper noble alloy and copper anode slime, and performing oxygen pressure acid leaching and copper removal: taking 250kg of high copper noble silver alloy to be treated and 1000kg of copper anode slime, crushing, uniformly mixing, press-filtering by a press filter, adding dilute sulfuric acid to carry out slurry mixing, controlling the liquid-solid ratio to be 4/1, adding the slurry into an oxygen autoclave to carry out oxygen pressure acid leaching, removing part of copper, lead and other impurity metals to obtain leaching liquid and leaching slag, and introducing the leaching slag into SO 2 And precipitating selenium to obtain selenium-precipitating slag and selenium-precipitating liquid. And (3) independently recycling selenium from the selenium-precipitated slag, adding copper powder into the selenium-precipitated liquid to precipitate tellurium, and obtaining copper telluride slag and the selenium-precipitated liquid, wherein the copper telluride slag is sent to a tellurium recycling process in an open circuit. And pumping the solution after tellurium precipitation to a decoppering process. Table 2 shows the element content in the leached residue after oxygen pressure acid leaching.
Table 2 shows the element content in the leached residue after oxygen pressure acid leaching
Step two, reduction smelting: adding the leaching slag obtained in the step one into a rotary top-blowing furnace, and adding scrap iron, white stone and coke powder/coal powder for reduction smelting. The scrap iron, the white stone and the silicon in the anode mud are used as slag-forming flux to form complex molten calcium silicate slag. After the materials are melted and fully reacted, the melt formed by final smelting is divided into two parts: the upper layer is smelting slag, and the lower layer is a noble lead alloy layer rich in Pb, sb, cu, bi, namely a noble lead alloy layer. In normal production, pb+Sb+Cu+Bi+Au+Ag in the noble lead alloy layer is more than or equal to 95 percent. The contents of the elements in the noble lead alloy and the smelting slag are shown in Table 3.
TABLE 3 noble lead alloy, content of elements in slag
Step three, oxidation converting: removing the upper layer smelting slag produced in the second step, keeping the Pb, sb, cu, bi noble alloy in the rotary top-blowing furnace, and introducing pressureAnd (5) oxidizing and converting the compressed air. The furnace temperature in the blowing process is controlled to 650 ℃, and the furnace temperature in the melting stage is maintained to be 1000 ℃ or above. Impurities such as Pb, sb and Bi are oxidized into oxides insoluble in Au and Ag in the blowing process, the oxides float on the surface of the melt slightly in specific gravity to form slag for removal, and the content of Ag in the preliminary blowing slag is usually controlled to be 0.7% or less. Se is oxidized into volatile selenate (SeO) during oxidation converting 2 ) In the blowing flue gas, au and Ag are usually further enriched into the gold-silver alloy phase in the oxidation blowing process, and the recovery rate of Ag in the blowing process is up to 98.5% or more. The contents of the elements in the blowing slag and the gold-silver alloy are shown in table 4.
TABLE 4 content of elements in slag and gold-silver alloy
Casting gold-silver alloy and SO 2 And (3) recycling selenium: and (3) scraping the blowing slag floating on the surface of the melt in the step three, casting the gold-silver alloy into an anode plate to form a silver anode plate, and conveying the silver anode plate to a silver anode plate electrolysis workshop. The silver anode contains 96% or more of silver and 1% of gold, and the content of impurities such as lead, antimony, bismuth, selenium and tellurium is controlled to be 100ppm or less.
Step five, flue gas treatment: smelting flue gas and the sodium selenate selenium-rich liquid generated in the third step, and then introducing SO 2 ，SO 2 And reducing and recovering selenium in the sodium selenate to form crude selenium. The elemental content of crude selenium is shown in table 5. The step is to obtain selenium-rich liquid and treated smoke dust, the selenium-rich liquid is sent to a selenium recovery process, and the treated smoke dust is returned to a smelting process.
TABLE 5 content of elements in anode plate and crude selenium
Example 2:
this example combines the treatment of the noble silver alloy and the copper anode slime, wherein the contents of the elements in the noble silver alloy and the copper anode slime to be treated are shown in table 6,
TABLE 6 elemental content of high copper noble silver alloy and copper anode slime to be treated
For the combined treatment process of the high-copper noble silver alloy and the copper anode slime, the specific steps are as follows:
step one, preprocessing high copper noble alloy and copper anode slime, and performing oxygen pressure acid leaching and copper removal: taking 250kg of high copper noble silver alloy to be treated and 1000kg of copper anode slime, crushing, uniformly mixing, press-filtering by a press filter, adding dilute sulfuric acid to carry out slurry mixing, controlling the liquid-solid ratio to be 4/1, adding the slurry into an oxygen autoclave to carry out oxygen pressure acid leaching, removing part of copper, lead and other impurity metals to obtain leaching liquid and leaching slag, and introducing SO into the leaching liquid 2 And (3) precipitating selenium to obtain selenium-precipitating slag and selenium-precipitating post-liquid, delivering the selenium-precipitating slag to a selenium recovery process, adding copper powder into the selenium-precipitating post-liquid to precipitate tellurium to obtain copper telluride slag and tellurium-precipitating post-liquid, delivering the copper telluride slag to a tellurium recovery process, and delivering the tellurium-precipitating post-liquid to a decoppering process.
Table 7 shows the element content in the leached residue after the oxygen pressure acid leaching.
Table 7 shows the element content in the leached residue after oxygen pressure acid leaching
Step two, reduction smelting: and (3) adding the leaching slag obtained in the step two into a rotary top-blowing furnace, and adding scrap iron, white stone and coke powder/coal powder for reduction smelting. The scrap iron, the white stone and the silicon in the anode mud are used as slag-forming flux to form complex molten calcium silicate slag. After the materials are melted and fully reacted, the melt formed by final smelting is divided into two parts: the upper layer is smelting slag, and the lower layer is a noble lead alloy layer rich in Pb, sb, cu, bi, namely a noble lead alloy layer. In normal production, pb+Sb+Cu+Bi+Au+Ag in the noble lead alloy layer is more than or equal to 95 percent. The contents of the elements in the noble lead alloy and the smelting slag are shown in Table 8.
TABLE 8 noble lead alloy, content of elements in slag of smelting
Step three, oxidation converting: and (3) scraping the upper layer smelting slag produced in the second step, and continuously keeping the Pb, sb, cu, bi noble alloy in a rotary top-blowing furnace, and introducing compressed air to perform oxidation blowing. The furnace temperature in the blowing process is controlled at 850 ℃, and the furnace temperature in the melting stage is kept above 1000 ℃. Impurities such as Pb, sb, bi and the like are oxidized into oxides which are insoluble in Au and Ag in the blowing process, the oxides have lighter specific gravity and float on the surface of a melt to form slag for removal, and the content of Ag in the preliminary blowing slag is controlled to be 0.7% or less. Se is oxidized into volatile selenate (SeO) during oxidation converting 2 ) And the Au and the Ag enter the blowing flue gas and are usually further enriched into a gold-silver alloy phase in the oxidation blowing process, and the recovery rate of the Ag in the blowing process is up to 98.5%. The contents of the respective elements in the blown slag and the gold-silver alloy are shown in Table 9.
TABLE 9 content of elements in slag and gold-silver alloy
Casting gold-silver alloy and SO 2 And (3) recycling selenium: and (3) scraping the blowing slag floating on the surface of the melt in the step three, casting the gold-silver alloy into an anode plate to form a silver anode plate, and conveying the silver anode plate to a silver anode plate electrolysis workshop. The silver anode contains more than 96% of silver and 2% of gold, and the content of impurities such as lead, antimony, bismuth, selenium, tellurium and the like is controlled to be 100ppm or less.
Step five, flue gas treatment: smelting flue gas and the third stepThe sodium selenate selenium-rich liquid generated in the process is introduced into SO 2 ，SO 2 And reducing and recovering selenium in the sodium selenate to form crude selenium. The elemental content of crude selenium is shown in table 10. The step is to obtain selenium-rich liquid and treated smoke dust, the selenium-rich liquid is sent to a selenium recovery process, and the treated smoke dust is returned to a smelting process.
TABLE 10 content of elements in anode plate and crude selenium
While the invention has been described and illustrated in considerable detail, it should be understood that modifications and equivalents to the above-described embodiments will become apparent to those skilled in the art, and that such modifications and improvements may be made without departing from the spirit of the invention.
Claims (6)
1. The combined treatment method of the high-copper high-silver alloy and the copper anode slime is characterized by comprising the following steps of:
step one, preprocessing copper anode slime: crushing and uniformly mixing high-copper noble silver alloy and copper anode slime, then carrying out filter pressing through a filter press, adding sulfuric acid and water for size mixing, then adding an oxygen autoclave for oxygen pressure acid leaching, removing part of copper and lead to obtain leaching liquid and leaching slag, and introducing SO into the leaching liquid 2 And (3) precipitating selenium to obtain selenium-precipitating slag and selenium-precipitating post-liquid, delivering the selenium-precipitating slag to a selenium recovery process, adding copper powder into the selenium-precipitating post-liquid to precipitate tellurium to obtain copper telluride slag and tellurium-precipitating post-liquid, delivering the copper telluride slag to a tellurium recovery process, and delivering the tellurium-precipitating post-liquid to a decoppering process.
Step two, reduction smelting: adding the leached slag obtained in the first step into a rotary top-blowing furnace, adding scrap iron, white stone and coke powder or coal dust for reduction smelting, taking silicon in the scrap iron, white stone and anode mud as a slag-forming flux to form multi-element complex melt calcium silicate slag, and after the materials are melted and fully reacted, dividing a melt formed by final smelting into two parts: the upper layer is smelting slag, and the lower layer is a precious lead alloy layer rich in Pb, sb, cu, bi, namely a precious lead alloy layer;
step three, oxidation converting: removing the upper smelting slag produced in the second step, keeping the lower noble lead alloy layer in a rotary top blowing furnace, and introducing compressed air to perform oxidation blowing to obtain high-copper blowing slag and gold-silver alloy;
casting gold-silver alloy and SO 2 And (3) recycling selenium: cleaning blowing slag floating on the surface of the melt in the third step, casting the gold-silver alloy into an anode plate to form a silver anode plate, and conveying the silver anode plate to a silver anode plate electrolysis workshop;
step five, flue gas treatment: and (3) introducing the smelting smoke from the second step and the converting smoke from the third step into a smoke treatment system to obtain selenium-rich liquid and treated smoke dust, wherein the selenium-rich liquid is sent to a selenium recovery process, and the treated smoke dust is returned to the smelting process.
2. The combined treatment method of the high-copper high-silver alloy and the copper anode slime, which is characterized in that the mass ratio of the high-copper high-silver alloy to the copper anode slime in the first step is 3:1-5:1.
3. The combined treatment method of the high-copper high-silver alloy and the copper anode slime according to claim 1, wherein the liquid-solid ratio of the slurry mixing in the first step is controlled to be 4/1.
4. The combined treatment method of the high-copper high-silver alloy and the copper anode slime, which is characterized in that the furnace temperature in the blowing process in the step three is controlled to be 650-850 ℃, and the furnace temperature in the melting stage is maintained to be more than 1000 ℃.
5. The method for combined treatment of high copper and high silver alloy and copper anode slime according to claim 1, wherein the silver anode plate in the fourth step contains more than 96% of silver and 1-2% of gold, and the content of impurities of lead, antimony, bismuth, selenium and tellurium is controlled below 100 ppm.
6. The combined treatment method of the high-copper high-silver alloy and the copper anode slime according to claim 1, wherein the flue gas in the fifth step is firstly introduced with NaOH to absorb SeO2 in the flue gas to generate sodium selenate selenium-rich liquid, then introduced with SO2, and the SO2 is reduced to recover selenium in the sodium selenate to form crude selenium.
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