CN112609078B - Copper anode mud treatment process - Google Patents
Copper anode mud treatment process Download PDFInfo
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- CN112609078B CN112609078B CN202011472722.9A CN202011472722A CN112609078B CN 112609078 B CN112609078 B CN 112609078B CN 202011472722 A CN202011472722 A CN 202011472722A CN 112609078 B CN112609078 B CN 112609078B
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- 238000000034 method Methods 0.000 title claims abstract description 103
- 239000010949 copper Substances 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000002893 slag Substances 0.000 claims abstract description 53
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 39
- 239000011669 selenium Substances 0.000 claims abstract description 39
- 238000003723 Smelting Methods 0.000 claims abstract description 38
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 27
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052788 barium Inorganic materials 0.000 claims abstract description 22
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007664 blowing Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 86
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 55
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- 238000002386 leaching Methods 0.000 claims description 29
- 239000000706 filtrate Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 10
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 9
- 238000009853 pyrometallurgy Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001698 pyrogenic effect Effects 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 238000012365 batch cultivation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
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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
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds 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
- 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
- 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
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- 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
-
- 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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Abstract
The invention discloses a copper anode mud treatment process, which belongs to the technical field of non-ferrous metal smelting and mainly comprises three process stages: (1) a step of wet decoppering, selenium and tellurium from anode slime; (2) wet deleading, barium and bismuth from anode mud; (3) a Calldo furnace pyrometallurgical stage. The process has the innovation points that: removing all copper, part of selenium and tellurium from the anode slime through a first process stage to produce corresponding copper, tellurium and selenium products; removing all lead, barium and bismuth in the second process stage to produce corresponding lead, barium and bismuth products; the impurities are removed through pretreatment in the first two process stages, a new anode mud Kaldo furnace pyrometallurgical treatment idea is provided, the smelting operation can be cancelled in the Kaldo furnace smelting stage, the blowing operation is carried out after the materials are directly melted, and the phenomenon that a large amount of precious metal-containing smelting slag (the output of the precious metal-containing smelting slag is generally 0.5-0.8 times of the weight of the anode mud) is produced in the conventional Kaldo furnace smelting operation is avoided.
Description
Technical Field
The invention belongs to the field of non-ferrous metal smelting, and particularly relates to a copper anode mud treatment process.
Background
The Kaldo furnace is initially applied to steel making, and is developed to be applied to non-ferrous metal smelting, and can treat copper concentrate, scrap copper, lead concentrate, scrap lead, lead dust, anode mud and the like. The use of Kaldo furnaces for anode slime treatment began in 1993, and about 10 Sikaldo furnaces are used for anode slime treatment in the world today. The technical process of anode mud treatment of Kaldo furnace mainly comprises the steps of pretreatment decoppering, smelting in Kaldo furnace and refining of gold and silver.
The pretreatment decoppering mainly comprises two processes: one is the traditional sulfating roasting and acid leaching decoppering process, the process needs to carry out roasting in a rotary kiln, roasted sand after roasting carries out acid leaching decoppering, and the process has the problem of toxic smoke dispersion; the other is an oxygen pressure leaching decoppering process, and the oxygen pressure high-temperature leaching decoppering is carried out by means of a high-pressure reaction kettle, so that the problem of high silver leaching rate exists, and noble metal dispersion is caused.
The process of treating the anode mud by the Kaldo furnace is mainly divided into 3 stages of smelting, converting and refining. The smelting process adopts batch feeding and batch smelting mode operation, and each furnace is fed with 2-3 batches of materials. The smelting operation needs to be carried out for a plurality of times of slag discharging, the smelting slag containing lead and barium is discharged, and the converting operation is carried out after the slag discharging is finished. The traditional treatment process needs to discharge a large amount of smelting slag containing precious metals, so that the direct recovery rate of the precious metals is reduced, the smelting slag needs to be subjected to subsequent treatment, the precious metals, lead, bismuth, barium and the like in the smelting slag are recovered, and the subsequent treatment cost is increased.
Disclosure of Invention
The invention aims to provide a copper anode slime treatment process, which does not adopt the existing pretreatment copper removal process, adopts atmospheric pressure leaching copper removal, adopts a conversion-leaching process to remove lead, barium and bismuth in anode slime in order to realize Kaldo furnace pyrometallurgy without a smelting stage, cancels the traditional smelting operation in the Kaldo furnace pyrometallurgy stage, directly carries out blowing and refining operation, and produces a gold-silver alloy.
Based on the purpose, the invention adopts the following technical scheme:
a copper anode mud treatment process mainly comprises three process stages: (1) a step of wet decoppering, selenium and tellurium from anode slime; (2) wet deleading, barium and bismuth from anode mud; (3) a Kaldo furnace pyrometallurgy stage.
(1) Wet decoppering of copper, selenium and tellurium from anode mud
Mixing anode mud into slurry, adding sulfuric acid and a medicament A after mixing the slurry, heating to control the temperature of the solution to be 50-90 ℃, adding a medicament B after the feed liquid reaches a preset temperature, continuing to react for 0.5-5 h after the medicament B is completely added, carrying out solid-liquid separation after the reaction is finished to obtain decoppered anode mud and a liquid containing copper, selenium and tellurium, and leading the decoppered anode mud to enter the next procedure to recover the copper, selenium and tellurium from the liquid;
(2) wet method for removing lead, barium and bismuth from anode mud
Primary sodium carbonate conversion procedure: the method comprises the steps of mixing the copper-removed anode slime, wherein liquid used for mixing is secondary sodium carbonate conversion filtering liquid, the part with insufficient liquid is supplemented by fresh water, sodium carbonate is added to control the concentration of sodium carbonate in a solution to be 100-200 g/l, the temperature is kept at 40-80 ℃, stirring is continuously carried out, reaction is carried out for 1-1.5 hours, solid-liquid separation is carried out on feed liquid to obtain filtrate and primary conversion slag, the filtrate is subjected to subsequent waste liquid treatment, and the primary conversion slag is subjected to secondary sodium carbonate conversion process treatment.
A secondary sodium carbonate conversion procedure: mixing the primary conversion slag, adding sodium carbonate after mixing, controlling the concentration of the sodium carbonate to be 200-300 g/l, keeping the temperature to be 40-80 ℃, reacting for 1-1.5 h under stirring, carrying out solid-liquid separation on feed liquid to obtain filtrate and secondary conversion slag, returning the filtrate to the primary sodium carbonate conversion process for mixing pulp, and feeding the secondary conversion slag into an acetic acid leaching process;
an acetic acid leaching process: adding water and secondary conversion slag into a reaction kettle, keeping the temperature at 50-60 ℃, adding acetic acid to adjust the pH of the feed liquid to 1.5-6, continuously stirring and reacting for 0.5-1 h, carrying out solid-liquid separation on the feed liquid, carrying out Kaldo furnace pyrogenic process treatment on filter residues, and carrying out lead and barium sulfate precipitation treatment on the filtrate;
(3) caldolo furnace pyrometallurgy
The first step is as follows: blowing selenium removal
The melt temperature is 1150-1200 ℃, slag is discharged once every 1.5-2.5 h of blowing, the end point of the selenium removal stage is judged according to the melt components, and the refining operation stage is started;
the second step is that: refining to remove copper and tellurium
Adding 0.1 t-0.2 t of flux into each ton of acetic acid leaching slag for oxidizing slagging, wherein the melt temperature is 1150-1200 ℃, deslagging is carried out every 1-1.5 h of converting, after deslagging, adding 0.1 t-0.2 t of flux into each furnace for continuously oxidizing slagging, and after all impurity elements in the alloy reach the silver electrolysis process requirements, ending the whole Kaldo furnace pyrometallurgy process, and entering a gold-silver recovery process after the gold-silver alloy is cast.
Further, in the step (1), sulfuric acid (industrial concentrated sulfuric acid with the concentration of more than 70 wt%) is added to control the content of sulfuric acid in the solution to be 10 g/L-150 g/L, and the agent A is a compound consisting of alkali metal and halogen elements; the concentration of the agent A in the solution is 1 g/L-10 g/L.
Further, the medicament B is one or a mixture of more than two of hydrogen peroxide (25 wt% -30 wt%), ferric sulfate and sodium ferrate in any proportion, and the dosage of the medicament B is 1.5-2 times of the theoretical mass dosage.
Further, the anode mud in the step (1) is subjected to slurry mixing according to the liquid-solid mass ratio of 3-5: 1; the sodium carbonate primary conversion procedure in the step (2): carrying out size mixing on the decoppered anode mud according to the liquid-solid mass ratio of 3-4: 1; a secondary sodium carbonate conversion procedure: mixing the primary conversion slag according to the liquid-solid ratio of 1.5-2: 1; an acetic acid leaching process: and adding water and secondary conversion slag into the reaction kettle, and controlling the liquid-solid mass ratio to be 1-3: 1.
Further, the specific process of the lead and barium sulfate precipitation process is as follows: adding a certain amount of sulfuric acid (more than 70wt% of industrial concentrated sulfuric acid) into the acetic acid leaching solution at normal temperature, continuously stirring and reacting for 0.5-1 h according to the condition that new precipitate is not produced in the solution, carrying out solid-liquid separation on the feed liquid, sending filter residues to a process of recovering lead and barium, and treating the filtrate in a bismuth precipitation process.
In the first step of the step (3), the selenium removing stage is carried out by blowing, no flux is added, the natural gas flow of the smelting gun is controlled to be 90 Nm/h, and the oxygen flow is controlled to be 250 Nm/h 3 H, controlling the instantaneous flow of compressed air of the converting spray gun to be 700-750 Nm 3 And h, keeping the temperature of the melt at 1150-1200 ℃, and rotating the furnace at 10-12 r/min to fully combine selenium in the melt with oxygen and enable the selenium to enter flue gas in the form of selenium oxide at high temperature.
In the second step of the step (3), 0.1 t-0.2 t of flux sodium carbonate is added into each ton of acetic acid leaching slag for oxidation slagging, the natural gas flow of a smelting gun is controlled to be 110Nm year/h, and the oxygen flow is 310Nm year/h 3 H, controlling the instantaneous flow of compressed air of the converting spray gun to be 700-750 Nm 3 Keeping the melt temperature at about 1200 ℃, rotating the furnace at 10-12 r/min, discharging slag every 1-1.5 h, adding 0.1-0.2 t of sodium carbonate per furnace after discharging slag, continuing oxidizing and slagging until all impurity elements in the alloy meet the requirements of silver electrolysis process (wherein Cu is less than or equal to 1%, Te is less than or equal to 0.01%, and Se is less than or equal to 0.01%), finishing the whole Kaldo furnace fire smelting process, and entering a gold and silver recovery process after casting the gold and silver alloy.
The process has the innovation points that: removing all copper, part of selenium and tellurium from the anode slime through a first process stage to produce corresponding copper, tellurium and selenium products; removing all lead, barium and bismuth in the second process stage to produce corresponding lead, barium and bismuth products; the impurities are removed through pretreatment in the first two process stages, a new anode mud Kaldo furnace pyrometallurgical treatment idea is provided, the smelting operation can be cancelled in the Kaldo furnace smelting stage, the blowing operation is carried out after the materials are directly melted, and the phenomenon that a large amount of precious metal-containing smelting slag (the output of the precious metal-containing smelting slag is generally 0.5-0.8 times of the weight of the anode mud) is produced in the conventional Kaldo furnace smelting operation is avoided.
The invention has the beneficial effects that: the process realizes the separation and recovery of the polymetallic and obtains the corresponding product; after the copper, the selenium, the tellurium, the lead, the barium and the bismuth are removed through pretreatment, the amount of anode mud is reduced to be less than half of the amount of raw materials, the processing capacity of the Kaldo furnace is improved, on one hand, a large amount of precious metal-containing smelting slag is not produced, the direct yield of gold, silver and platinum group elements is improved, the dispersion of precious metals is avoided, on the other hand, the pyrometallurgical smelting time of the Kaldo furnace is shortened, the processing capacity of the Kaldo furnace is further improved, the subsequent processing of the smelting slag of the Kaldo furnace is cancelled, and the production cost is reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The liquid-solid ratio in the present application means a mass ratio.
Example 1
A copper anode slime treatment process is shown in figure 1 and comprises the following steps:
(1) wet decoppering of copper, selenium and tellurium from anode mud
Taking 5t of 1# anode mud (the components of which are shown in the table) to carry out size mixing according to a liquid-solid ratio of 3:1, adding industrial concentrated sulfuric acid after size mixing to control the content of sulfuric acid in the solution to be about 100g/L, adding a catalyst KI to control the concentration to be 1g/L, introducing steam to heat to 70 ℃, adding 30wt% hydrogen peroxide, wherein the usage amount of the hydrogen peroxide is 1.8 times of the theoretical mass usage amount, continuing to react for 2 hours after all hydrogen peroxide is added, and filtering by using a plate frame to obtain 4.15t of decoppered anode mud and a solution containing copper, selenium and tellurium, wherein the solution contains 38g/L of copper, 1.8g/L of selenium and 3.3g/L of tellurium, and the main components of the decoppered anode mud are shown in the table:
(2) wet method for removing lead, barium and bismuth from anode mud
The first step is as follows: and a primary sodium carbonate conversion process. And (2) carrying out size mixing on the decoppered anode slime obtained in the process stage (1) according to a liquid-solid ratio of 3:1, wherein liquid used for size mixing is 5m sodium bicarbonate conversion filtration liquid, fresh water is supplemented by 5.5m, solid sodium carbonate is supplemented to control the concentration of the solution sodium carbonate to be 150g/L, the temperature is kept at 70 ℃, stirring is carried out continuously, reaction is carried out for 1.5h, solid-liquid separation is carried out on feed liquid by a plate frame, subsequent waste liquid treatment is carried out on filtrate obtained by 10.5m during powder cultivation, and 3.8t filter residue (primary conversion residue) enters a sodium bicarbonate conversion process for treatment.
The second step is that: and a sodium bicarbonate conversion process. 3.8t of primary sodium carbonate conversion slag is subjected to size mixing according to a liquid-solid ratio of 2:1, solid sodium carbonate is added after size mixing, the concentration of the sodium carbonate is controlled to be 250g/l, the temperature is kept at 80 ℃, stirring is continuously performed, after reaction is performed for 1h, solid-liquid separation is performed on feed liquid, 5m of filtrate obtained from top-dressing is returned to the primary sodium carbonate conversion process for size mixing, 3.55t of filter residue (secondary conversion slag) enters an acetic acid leaching process for treatment, and the main components of the secondary conversion slag are shown in the following table:
the third step: and (5) an acetic acid leaching process. Adding 8m new water and 3.55t secondary transformation slag into the reaction kettle, controlling the liquid-solid ratio to be 3:1, keeping the temperature to be 50-60 ℃, adding industrial acetic acid to adjust the pH value of the feed liquid to be 5.2, continuously stirring for reaction for 1h, carrying out solid-liquid separation on the feed liquid, carrying out Kaldo furnace fire method treatment on 0.9t filter residue, and carrying out lead sulfate precipitation and barium sulfate treatment on 10m filtrate.
The fourth step: and (5) depositing lead and barium by sulfuric acid. Adding industrial sulfuric acid into the acetic acid leaching solution obtained by ethanol production at normal temperature and 10m, continuously stirring and reacting for 0.5-1 h according to the condition that new precipitates are not produced any more in the solution, carrying out solid-liquid separation on feed liquid, sending 2.7t filter residues to a process of recovering lead and barium, carrying out treatment on the filter residues containing 57.5wt% of lead and 10.3wt% of barium, and sending filtrate obtained by ethanol production at 10m into a bismuth precipitation process for treatment, wherein the filtrate contains 9.1g/L of bismuth.
(3) Caldolo furnace pyrometallurgy
The first step is as follows: selenium removal in converting operations
A blowing selenium removal stage, wherein acetic acid leaching slag obtained in the process stage (2) is added into a Kaldo furnace for carrying out thin film transformation in batches when certain weight is accumulated, the materials are firstly melted without adding any flux, the natural gas flow of a smelting gun is controlled to 90 Nm/h, the oxygen flow is 250 Nm 3 H, controlling the instantaneous flow of compressed air of the converting spray gun to be 700Nm 3 The temperature of the melt is kept between 1150 and 1200 ℃, the rotating speed of the furnace is 10 to 12r/min,selenium in the melt is fully combined with oxygen and enters the flue gas in the form of selenium oxide at high temperature. And (4) deslagging once every 2h of blowing, judging the end point of the selenium removal stage according to the components of the melt, and entering the refining operation stage.
The second step is that: refining operation for removing copper and tellurium
Adding 0.1t of sodium carbonate into 1t of acetic acid leaching slag for oxidizing slagging, controlling the natural gas flow of a smelting gun to be 110 Nm/h, and controlling the oxygen flow to be 310 Nm/h 3 H, controlling the instantaneous flow of compressed air of the converting spray gun to be 730Nm 3 Keeping the melt temperature at about 1200 ℃, rotating the furnace at 10-12 r/min, discharging slag every 1-1.5 h, adding 0.2t of flux sodium carbonate after slag discharge, continuing to oxidize and slag until all impurity elements in the alloy meet the requirements of silver electrolysis process (wherein Cu is less than or equal to 1%, Te is less than or equal to 0.01%, and Se is less than or equal to 0.01%), finishing the whole Kaldo furnace pyrometallurgical smelting process, casting the obtained gold-silver alloy, and then entering a gold-silver recovery process, wherein the gold content of the alloy is 5.14wt%, the silver content is 88.56wt%, the recovery rate of gold is higher than 99.5%, and the recovery rate of silver is higher than 99%.
Example 2
A copper anode slime treatment process is shown in figure 1 and comprises the following steps:
(1) wet decoppering of copper, selenium and tellurium from anode mud
Taking 5t of 1# anode mud (the components of which are shown in the table) to carry out size mixing according to a liquid-solid ratio of 3:1, adding industrial concentrated sulfuric acid after size mixing to control the content of sulfuric acid in the solution to be about 150g/L, adding a catalyst NaCl to control the concentration to be 5g/L, introducing steam to be added to 70 ℃, adding sodium ferrate, wherein the usage amount of the sodium ferrate is 1.4 times of the theoretical mass usage amount, continuing to react for 4 hours after the sodium ferrate is completely added, and filtering by using a plate frame to obtain 4.2t of decoppered anode mud and a solution containing copper, selenium and tellurium in a weight ratio of 13.5m, wherein the solution contains 46g/L of copper, 2.3g/L of selenium and 4.1g/L of tellurium, and the main components of the decoppered anode mud are shown in the table:
(2) wet method for removing lead, barium and bismuth from anode mud
The first step is as follows: and a primary sodium carbonate conversion process. And (2) carrying out size mixing on the 4.2t decoppered anode slime obtained in the process stage (1) according to a liquid-solid ratio of 3:1, wherein the liquid used for size mixing is a 4.8m sodium carbonate twice conversion filtration liquid, replenishing fresh water by 6m, replenishing solid sodium carbonate to control the concentration of the solution sodium carbonate to be 100g/L, keeping the temperature to be 60 ℃, continuously stirring, reacting for 1h, carrying out plate-frame solid-liquid separation on feed liquid, carrying out subsequent waste liquid treatment on 11m pulp filtrate, and carrying out sodium carbonate twice conversion treatment on 3.85t filter residues (primary conversion residues).
The second step is that: and a sodium bicarbonate conversion process. 3.85t of primary sodium carbonate conversion slag is subjected to size mixing according to the liquid-solid ratio of 1.5:1, solid sodium carbonate is added after size mixing, the concentration of the sodium carbonate is controlled to be 250g/l, the temperature is kept at 70 ℃, continuous stirring is carried out, after reaction is carried out for 1h, solid-liquid separation is carried out on feed liquid, 4.8m of filtrate obtained after the pulp mixing is carried out is returned to the primary sodium carbonate conversion process for size mixing, 3.74t of filter residue (secondary conversion slag) enters the acetic acid leaching process for treatment, and the main components of the secondary conversion slag are shown in the following table:
the third step: and (5) an acetic acid leaching process. Adding 7.5m of fresh water and 3.74t of secondary transformation slag into a reaction kettle, controlling the liquid-solid ratio to be 3:1, keeping the temperature to be 50-60 ℃, adding industrial acetic acid to adjust the pH value of the feed liquid to be 4.5, continuously stirring and reacting for 1h, carrying out solid-liquid separation on the feed liquid, carrying out Kaldo furnace fire treatment on 1.2t of filter residue, and carrying out lead sulfate precipitation and barium sulfate precipitation on 10.5m of filtrate obtained by powder chromatography.
The fourth step: and (5) depositing lead and barium by sulfuric acid. Adding industrial concentrated sulfuric acid into the acetic acid leaching solution at the normal temperature of 10.5m, continuously stirring and reacting for 0.5-1 h according to the condition that new precipitates are not produced any more in the solution, carrying out solid-liquid separation on the feed liquid, sending 2.6t filter residues to a process of recovering lead and barium, carrying out treatment on the filter residues containing 54.7wt% of lead and 11.6wt% of barium, and carrying out treatment on 10.5m filtrate by powder milling to a bismuth precipitation process, wherein the filtrate contains 8.4g/L of bismuth.
(3) Caldolo furnace pyrometallurgy
The first step is as follows: selenium removal in converting operations
A stage of blowing selenium removal, namely the vinegar obtained in the process stage (2)When the acid leaching slag is accumulated to a certain weight, adding the acid leaching slag into a Kaldo furnace for carrying out batch cultivation in 0.8m, carrying out material transformation firstly without adding any flux, controlling the natural gas flow of a smelting gun to be 90 Nm/h, and controlling the oxygen flow to be 250 Nm/h 3 H, controlling the instantaneous flow of the converting air of the converting spray gun to be 700-750 Nm 3 And h, keeping the temperature of the melt at 1150-1200 ℃, and rotating the furnace at 10-12 r/min to fully combine selenium in the melt with oxygen and enable the selenium to enter flue gas in the form of selenium oxide at high temperature. And (4) deslagging once every 2h of blowing, judging the end point of the selenium removal stage according to the components of the melt, and entering the refining operation stage.
The second step is that: refining operation for removing copper and tellurium
Adding 0.12t of sodium carbonate into 1t of acetic acid leaching slag for oxidizing slagging, controlling the natural gas flow of a smelting gun to be 110 Nm/h, and controlling the oxygen flow to be 310 Nm/h 3 H, controlling the instantaneous flow of the compressed air of the blowing spray gun to be 700Nm 3 Keeping the melt temperature at about 1200 ℃, rotating the furnace at 10-12 r/min, discharging slag every 1-1.5 h, adding 0.1t of sodium carbonate after discharging slag, continuing to oxidize and slag until all impurity elements in the alloy meet the requirements of silver electrolysis process (wherein Cu is less than or equal to 1%, Te is less than or equal to 0.01%, and Se is less than or equal to 0.01%), finishing the whole Kaldo furnace pyrometallurgical smelting process, casting the obtained gold-silver alloy, and then entering a gold-silver recovery process, wherein the alloy contains 10.12% of gold, contains 85.42% of silver, the recovery rate of gold is higher than 99.5%, and the recovery rate of silver is higher than 99.0%.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.
Claims (8)
1. A copper anode slime treatment process is characterized by comprising the following steps:
(1) wet decoppering of copper, selenium and tellurium from anode mud
Mixing anode mud into slurry, adding sulfuric acid and a medicament A after mixing the slurry, heating to control the temperature of the solution to be 50-90 ℃, adding a medicament B after the feed liquid reaches a preset temperature, continuing to react for 0.5-5 h after the medicament B is completely added, carrying out solid-liquid separation after the reaction is finished to obtain decoppered anode mud and a liquid containing copper, selenium and tellurium, and leading the decoppered anode mud to enter the next procedure to recover the copper, selenium and tellurium from the liquid; the medicament A is a compound consisting of alkali metal and halogen element; the medicament B is one or a mixture of more than two of hydrogen peroxide, ferric sulfate and sodium ferrate in any proportion;
(2) wet anode slime deleading, barium and bismuth
Primary sodium carbonate conversion procedure: mixing the copper-removed anode mud, adding sodium carbonate to control the concentration of sodium carbonate in a solution to be 100-200 g/l, keeping the temperature to be 40-80 ℃, reacting for 1-1.5 h under stirring, carrying out solid-liquid separation on feed liquid to obtain filtrate and primary conversion slag, and carrying out subsequent waste liquid treatment on the filtrate;
a secondary sodium carbonate conversion procedure: mixing the primary conversion slag, adding sodium carbonate after mixing, controlling the concentration of the sodium carbonate to be 200-300 g/l, keeping the temperature to be 40-80 ℃, reacting for 1-1.5 h under stirring, carrying out solid-liquid separation on feed liquid to obtain filtrate and secondary conversion slag, returning the filtrate to the primary sodium carbonate conversion process for mixing pulp, and feeding the secondary conversion slag into an acetic acid leaching process;
an acetic acid leaching process: adding water and secondary conversion slag into a reaction kettle, keeping the temperature at 50-60 ℃, adding acetic acid to adjust the pH of the feed liquid to 1.5-6, continuously stirring and reacting for 0.5-1 h, carrying out solid-liquid separation on the feed liquid, carrying out Kaldo furnace pyrogenic process treatment on filter residues, and carrying out lead and barium sulfate precipitation treatment on the filtrate;
(3) caldolo furnace pyrometallurgy
The first step is as follows: blowing selenium removal
The melt temperature is 1150-1200 ℃, slag is discharged once every 1.5-2.5 h of blowing, the end point of the selenium removal stage is judged according to the melt components, and the refining operation stage is started;
the second step is that: refining to remove copper and tellurium
Adding 0.1 t-0.2 t of flux into each ton of acetic acid leaching slag for oxidizing slagging, wherein the melt temperature is 1150-1200 ℃, deslagging is carried out every 1-1.5 h of converting, after deslagging, adding 0.1 t-0.2 t of flux into each furnace for continuously oxidizing slagging, and after all impurity elements in the alloy reach the silver electrolysis process requirements, ending the whole Kaldo furnace pyrometallurgy process, and entering a gold-silver recovery process after the gold-silver alloy is cast.
2. The copper anode slime treatment process according to claim 1, wherein in the step (1), sulfuric acid is added to control the sulfuric acid content in the solution to be 10-150 g/L, and the concentration of the agent A in the solution is 1-10 g/L.
3. The copper anode slime treatment process according to claim 1, wherein the dosage of the agent B is 1.5-2 times of the theoretical mass dosage.
4. The copper anode slime treatment process according to claim 1, wherein in the step (1), the anode slime is subjected to size mixing according to a liquid-solid mass ratio of 3-5: 1; the sodium carbonate primary conversion procedure in the step (2): carrying out size mixing on the decoppered anode mud according to the liquid-solid mass ratio of 3-4: 1; a secondary sodium carbonate conversion procedure: mixing the primary conversion slag according to the liquid-solid ratio of 1.5-2: 1; an acetic acid leaching process: and adding water and secondary conversion slag into the reaction kettle, and controlling the liquid-solid mass ratio to be 1-3: 1.
5. The copper anode slime treatment process according to claim 1, wherein the specific processes of the lead and barium sulfate precipitation procedures are as follows: adding sulfuric acid into the acetic acid leaching solution at normal temperature, continuously stirring and reacting for 0.5-1 h according to the addition amount of the sulfuric acid without producing new precipitates, carrying out solid-liquid separation on feed liquid, conveying filter residues to a working procedure of recovering lead and barium, and treating filtrate in a bismuth precipitation working procedure.
6. The copper anode slime treatment process according to claim 1, wherein in the first step of step (3), the natural gas flow is controlled to 90 +/-5 Nm/h, the volume ratio of oxygen to natural gas of a smelting gun is 2.5-3.0: 1, and the instantaneous compressed air flow of a blowing spray gun is controlled to 700-750 Nm 3 H; in the second step, controlling the natural gas flow to be 110 +/-10 Nm/h, controlling the volume ratio of oxygen to natural gas of a smelting gun to be 2.5-3.0: 1, and controlling the instantaneous flow of compressed air of a blowing spray gun to be 700-750 Nm/h 3 /h 。
7. The copper anode slime treatment process according to claim 1, wherein the flux in step (3) is sodium carbonate.
8. The copper anode slime treatment process according to claim 1, wherein in the second step of step (3), the impurity elements meet the silver electrolysis process requirements as follows: cu is less than or equal to 1wt%, Te is less than or equal to 0.01 wt%, and Se is less than or equal to 0.01 wt%.
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| CN114672661A (en) * | 2022-03-04 | 2022-06-28 | 金川集团股份有限公司 | Method for judging precious metal smelting converting end point of Kaldo furnace |
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