LU507646B1 - Method for recovering lead, antimony and tin from complex lead-antimony hazardous waste materials - Google Patents
Method for recovering lead, antimony and tin from complex lead-antimony hazardous waste materials Download PDFInfo
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- LU507646B1 LU507646B1 LU507646A LU507646A LU507646B1 LU 507646 B1 LU507646 B1 LU 507646B1 LU 507646 A LU507646 A LU 507646A LU 507646 A LU507646 A LU 507646A LU 507646 B1 LU507646 B1 LU 507646B1
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- lead
- antimony
- tin
- waste materials
- hazardous waste
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 106
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002893 slag Substances 0.000 claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 33
- 239000002140 antimony alloy Substances 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- QQHJESKHUUVSIC-UHFFFAOYSA-N antimony lead Chemical compound [Sb].[Pb] QQHJESKHUUVSIC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 9
- 239000003245 coal Substances 0.000 claims abstract description 8
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 6
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims description 50
- 229910052745 lead Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910004074 SiF6 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 16
- 229910000410 antimony oxide Inorganic materials 0.000 description 9
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001208 Crucible steel Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/06—Refining
-
- 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
-
- 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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- C22B25/00—Obtaining tin
- C22B25/08—Refining
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
-
- 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
- C22B7/04—Working-up slag
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Acoustics & Sound (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials comprises: (1) side-blown reduction smelting: adding a certain amount of gangue and reduced coal into complex hazardous waste materials containing lead and antimony, and putting them into a side-blown reduction furnace for reduction smelting to obtain an alloy; (2) separating tin: putting the alloy discharged from the side blowing reduction furnace into a stainless steel anode pot, heating and stirring to remove tin; (3) separating copper: further lowering the temperature of the alloy after stirring to remove tin, adding xylose, stirring and removing slag to obtain lead-antimony alloy with copper content less than 0.2%, and casting the lead-antimony alloy anode plate; (4) electrolytic refining: the lead-antimony anode plate is put into a lead electrolytic cell for electrolysis, and refined lead ingots are produced after ingot casting.
Description
DESCRIPTION HUS07646
METHOD FOR RECOVERING LEAD, ANTIMONY AND TIN FROM COMPLEX
LEAD-ANTIMONY HAZARDOUS WASTE MATERIALS
The invention relates to the technical field of pyrometallurgy, in particular to a method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials.
According to the characteristics of antimony-lead-containing complex hazardous waste materials, the traditional methods for treating these materials are as follows: 1. the lead slag-removed produced by antimony smelting and refining is crushed, ball-milled and alkali-leached to obtain phosphorus-containing high-lead antimony oxide, and then the phosphorus-containing high-lead antimony oxide is put into a reverberatory furnace for reduction to obtain high-lead antimony, and the high-lead antimony is continuously circulated by swing-reduction-swing-reduction to finally obtain antimony and lead.
However, the separation of antimony and lead is not complete. 2. The small antimony smelter directly puts lead-containing antimony slag into blast furnace, and adds flux iron ore, flux sodium carbonate, coking coal, etc. After high temperature oxidation, reduction, oxidation and other processes, the antimony and lead in the feed volatilized and combined together to obtain high lead antimony oxide. Next, puts the high lead antimony oxide into reverberatory furnace for reduction to obtain high-lead antimony. After that, the high-lead antimony is put into swing furnace, and through the continuous cycle of swing-reduction-swing-reduction, antimony oxide and lead are finally obtained, but the separation of lead and antimony is also not complete.
Additionally, for this method, the treatment process is long, time-consuming, the 507646 treatment cost is high, and there is no profit space.
CN201811348203 discloses a method for pyrometallurgical separation of antimony and lead from lead-containing antimony slag, which comprises the following steps: the lead-containing antimony slag is crushed, and the reducing agent is added and mixed evenly, then the mixed material is heated and melted in a medium-frequency induction furnace, after cooling reaction, the antimony liquid is poured out and the ingot is cast, and the antimony ingot is finally obtained. The disadvantages of this method are small processing capacity, large energy consumption and high production cost.
CN105603197A discloses a reverberatory furnace treatment method for antimony slag or antimony dust, which is similar to treating antimony slag by adding flux iron ore, flux sodium carbonate, coking coal, etc. in a blast furnace. Although antimony is reduced, other impurity metals are also reduced, which has no effect on the separation of antimony and impurity metals. A large amount of iron ore and stones should be added for slagging, which further wastes the resources of iron ore and stones and increases the cost of storage and reprocessing of waste residue.
CN101538658A discloses a new smelting process of antimony oxide slag. The antimony oxide slag is treated in the blast furnace of smelting lead-antimony alloy, and the antimony oxide is volatilized from the slag at high temperature and low pressure.
However, when antimony oxide is volatilized, impurities such as lead oxide are volatilized at the same time, and the effectively separation of lead and antimony cannot be achieved. In order to realize the effectively separation of lead and antimony, it is also necessary to adopt a continuous cycle process of reduction-oxidation-reduction-oxidation, which is time-consuming and energy consuming, it is not suitable for the treatment of lead antimony slag.
CN1908208A discloses a process for comprehensively recovering valuable metals from antimony oxychloride slag. Although antimony can be effectively separated from the slag, there are still technical defects such as long blowing time and high energy consumption.
In summary, the effective and rapid treatment of antimony-lead-containing complex 0 040 hazardous waste materials has been studied for a long time, but no new technology has been found that can quickly and effectively react with materials, efficiently separate antimony and lead, adapt to a variety of different hazardous wastes with a single equipment, and has the advantages of low cost, high profit, short process, convenient operation, and new environmental protection.
The purpose of the invention is to solve the above technical problems, and to provide a method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials, so as to produce tin products, copper products, lead products and antimony products respectively, and a single device is suitable for a variety of hazardous wastes, thus greatly reducing the production cost and shortening the production cycle.
In order to achieve the above purpose, the technical scheme of the invention is as follows.
A method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials: (1) side-blown reduction smelting: a certain amount of gangue and reduced coal mixed with hazardous waste materials, and then putting into a side-blown reduction furnace for reduction smelting, wherein the reduction temperature is controlled at 1100-1300 °C, and the reduction time is 60-90 min, so that the upper slag contains 2-4% of valuable metals, and the alloy and slag are discharged from different furnace mouths after smelting is completed; (2) separating tin: putting the alloy discharged from the side-blown reduction furnace into a stainless steel anode pot, raising the temperature to 750-800 °C, putting into a blender to stir the metal for 1.5 to 2 h, additionally, salt is added into the pot to form a film to avoid metal volatilization loss, and finally taking out tin slag to obtain the alloy after stirring and tin removal;
(3) separating copper. lowering the temperature of the alloy after stirring ang 07040 removing tin to 500-400 °C, adding xylose, stirring and removing slag for 2-5 times, and the whole process lasts for 1.5 to 2 h to obtain lead-antimony alloy with copper content less than 0.2%, and casting the lead-antimony alloy anode plate; (4) electrolytic refining: putting the lead-antimony anode plate into the lead electrolytic tanks for electrolysis, and the current density of electrolysis is controlled at 150 A/m? and below, then ingot casting the precipitated cathode lead to obtain refined lead ingot, and obtaining anode mud containing 60% antimony for recovering antimony products.
The total grade of valuable nonferrous metals in the raw materials is more than 10%, and the sulfur content in the raw materials does not exceed 5%.
Unless otherwise specified, the percentages mentioned in the invention are all mass percentages, and the sum of the percentages of each component is 100%.
The invention has the following advantages
The invention can produce qualified refined lead, tin slag containing more than 30% tin and anode mud containing more than 60% antimony. Single equipment adapts to a variety of different hazardous waste materials, greatly reducing production costs and short production cycle.
Fig. 1 is a process flow chart of the method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials.
In the following, the technical scheme of the present invention will be described in detail with examples, but the implementation of the present invention is not limited to the scope indicated by the examples.
Embodiment 1
This embodiment provides a method for recovering lead, antimony and tin from 907646 antimony-lead-containing complex hazardous waste materials, including the following steps:
S1, the 10% of reduced coal was added to the antimony-lead-containing complex hazardous waste materials containing 40% lead, 10% antimony and 2% tin to obtain a mixed material. Then, the mixed material was evenly putting into an 8.4 m? side-blown reduction furnace through a feeding belt (feeding 30 tons in 20 min), then reduction smelting was performed at 1200°C for 70 min. After the reduction, the alloy and slag were discharged from different furnace mouths respectively, and the furnace was put out for 25 min to produce 12 tons of coarse lead-antimony alloy containing 83% lead, 14% antimony and 2% tin, and 15 tons of slag containing 1.8% lead, 1.4% antimony and 0.3% tin. The above steps were repeated 5 times until produced 50 tons lead-antimony crude alloy.
S2, putting 50 tons of the lead-antimony crude alloy into a stainless steel anode pot with a capacity of 1 m3, and natural gas was used to raise temperature to 800°C, putted it into a blender for 1.5 h, and 30 kilograms of salt were added into the pot, then took out 3 tons of tin slag, which containing 32% Sn, 8% Pb and 2% Sb, and the lead-antimony crude alloy liquid was obtained after removing the tin slag.
S3, lead-antimony crude alloy liquid removed from the tin slag was extracted by a lead pump and injected into another cast steel anode pot, and the temperature was slowly lowered to 450°C under the stirring state. During this period, when there was scum on the surface of the alloy liquid, it was removed. The whole stirring time was 90 min, 1 ton of copper slag (containing 15% Cu, 55% Pb and 15% Sb) was removed, and the lead-antimony coarse alloy liquid was obtained after removing the copper slag;
S4, casting lead-antimony alloy anode plates from the lead-antimony crude alloy liquid after copper slag fishing, wherein the lead-antimony alloy anode plates contains 82% Pb, 16% Sb and 0.2% Cu, and placing the lead-antimony alloy anode plates into lead electrolytic tanks for electrolysis, wherein each lead-antimony alloy anode plate weighs 90 Kg, and each tank was filled with 35 lead-antimony alloy anode plates, and the current density was 150 A/m?, and the electrolyte composition were: H2SiFe (total)
115.08 g/L, Pb? 42.77 g/L. H.SiFs (swim) 85.33 g/L, electrifying time: 70 h. The 9/46 precipitated lead satisfied with the national standard of O# refined lead, and the anode mud contains 15% Pb, 62% Sb and 1.5% Cu.
Embodiment 2
This embodiment provides a method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials, including the following steps:
S1, hazardous waste materials containing lead (25%), antimony (8%) and tin (1%) were mixed into 10% of reduced coal, and then evenly added into a 8.4 m? side-blown reduction furnace through a feeding belt, and 30 tons were fed within 20 min, and then reduction smelting was carried out at 1180°C for 60 min. After the reduction, the alloy and slag were discharged from different furnace mouths respectively, and the furnace was put out for 25 min, so that 9 tons of coarse lead-antimony alloy containing 81% lead, 16% antimony and 1.5% tin were produced, and 18 tons of slag containing 1.8% lead, 1.4% antimony and 0.3% tin were produced. The above steps were repeated 6 times until produced 50 tons lead-antimony crude alloy.
S2, putting 50 tons of lead-antimony crude alloy discharged from the side-blown reduction furnace into a stainless steel anode pot with a capacity of 1 m3, and natural gas was used to raise temperature to 800°C, putted it into a blender for 1.5 h, and 30 kilograms of salt were added into the pot, then took out 2 tons of tin slag, which containing 36% Sn, 5% Pb and 2% antimony, and the lead-antimony crude alloy liquid was obtained after removing the tin slag.
S3, lead-antimony crude alloy liquid from which the tin slag was removed was extracted by a lead pump and injected into another cast steel anode pot, and the temperature was slowly lowered to 450°C under the stirring state. During this period, when there was scum on the surface of the alloy liquid, it was removed.
The whole stirring time was 100 min, 1 ton of copper slag (containing 12% Cu, Go 507646
Pb and 17% Sb) was removed, and the lead-antimony coarse alloy liquid was obtained after removing the copper slag;
S4, casting lead-antimony alloy anode plates from the lead-antimony crude alloy liquid after copper slag fishing, wherein the lead-antimony alloy anode plates contains 82% Pb, 16% Sb and 0.2% Cu, and placing the lead-antimony alloy anode plates into lead electrolytic tanks for electrolysis, wherein each lead-antimony alloy anode plate weighs 90 Kg, and each tank was filled with 35 lead-antimony alloy anode plates, and the current density was 150 A/m?, and the electrolyte composition were: H2SiFe (total) 112.08 g/L, Pb?" 45.71 g/L, H:SiFe (swim) 88.23 g/L, electrifying time: 70 h. The precipitated lead satisfied with the national standard of O# refined lead, and the anode mud contains 12% Pb, 65% Sb and 1.8% Cu.
Embodiment 3
This embodiment provides a method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials, including the following steps:
S1: Mixing hazardous lead-antimony waste materials containing 20% lead, 5% antimony and 1% tin into 10% reduced coal, uniformly put them into a 8.4 m? side-blown reduction furnace through a feeding belt, feed 30 tons in 20 min, and then carried out reduction smelting at 1150°C for 65 min. After the reduction, the alloy and slag were discharged from different furnace mouths respectively, and the furnace was put out for min, and 6.7 tons of lead-antimony coarse alloy containing 82.5%, antimony 15.6% and tin 2.1% were produced, and 20.5 tons of slag containing 1.8%, antimony 1.4% and tin 0.3% were produced. These steps were repeated for 8 times until 50 tons of lead-antimony coarse alloy was produced.
S2, putting 50 tons of lead-antimony crude alloy discharged from the side-blowr 07/646 reduction furnace into a stainless steel anode pot with a capacity of 1 cubic meter, the temperature was raised to 800 °C with natural gas, then a stirrer was putted for stirring for 100 min, and 30 kilograms of salt were added into the pot, and then 2.7 tons of tin slag containing 36.5% of Sn, 5.5% of Pb and 2.1% of Sb were removed to obtain lead-antimony crude alloy liquid;
S3, pumping out the lead-antimony coarse alloy liquid from which the tin slag was removed by a lead pump, injecting it into another cast steel anode pot, slowly cooling to 450 °C under the stirring state, and taking out the liquid when there was scum on the surface during the whole stirring time of 100 min, and taking out 1 ton of copper slag containing 16.5% of Cu, 66.1% of Pb and 16.7% of Sb to obtain the lead-antimony coarse alloy liquid from which the copper slag was removed;
S4, casting lead-antimony alloy anode plates from the lead-antimony crude alloy liquid after copper slag fishing, wherein the lead-antimony alloy anode plates contain 82% of Pb, 16% of Sb and 0.2% of Cu, and putting the lead-antimony alloy anode plates into lead electrolytic tanks for electrolysis, wherein each lead-antimony alloy anode plate weighs 90Kg, and each tank contains 35 lead-antimony alloy anode plates, and the current density was 145 A/m?, and electrolyte composition: H2SiFe (total) 118.18 g/L,
Pb?" 46.87 g/L, H:SiF6 (swim) 88.37 g/L, electrifying time: 65 h, the precipitated lead satisfied with the national standard of O# refined lead, and the anode mud contains 12.1% Pb, 66.4% Sb and 1.7% Cu.
The above-mentioned embodiments are only specific examples for further explaining the purpose, technical scheme and beneficial effects of the present invention, and the present invention is not limited thereto. Any modification, equivalent substitution, improvement, etc. made within the disclosed scope of the present invention are included in the protection scope of the present invention.
Claims (10)
1. A method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials, comprising: (1) side-blown reduction smelting: adding a certain amount of gangue and reduced coal into complex hazardous waste materials, and then putting into a side-blown reduction furnace for reduction smelting, wherein the reduction temperature is controlled at 1100-1300C, and the reduction time is 60-90 min, so that the upper slag contains 2-4% of valuable metals, and the alloy and slag are discharged from different furnace mouths after smelting is completed; (2) separating tin: putting the alloy discharged from the side-blown reduction furnace into a stainless steel anode pot, raising the temperature to 750-800°C, putting into a blender to stir the metal for 1.5 to 2 h, adding salt into the pot to form a film to avoid metal volatilization loss, and finally taking out tin slag to obtain the alloy after stirring and tin removal; (3) separating copper. lowering the temperature of the alloy after stirring and removing tin to 500-400°C, adding xylose, stirring and removing slag for 2-5 times, wherein the whole process lasts for 1.5 to 2 h to obtain lead-antimony alloy with copper content less than 0.2%, and casting the lead-antimony alloy anode plate; (4) electrolytic refining: putting the lead-antimony anode plate into the lead electrolytic tanks for electrolysis, controlling the current density of electrolysis at 150 A/m?, then ingot casting the precipitated cathode lead to obtain refined lead ingot, and obtaining anode mud containing 60% antimony for recovering antimony products.
2. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that the total grade of valuable nonferrous metals in the raw materials is more than 10%, and the sulfur content in the raw materials is not more than 5%.
3. The method for recovering lead, antimony and tin from antimony-lead-containing >. /$46 complex hazardous waste materials according to claim 1, characterized in that the complex hazardous waste materials containing lead and antimony are hazardous waste materials containing 40% lead, 10% antimony and 2% tin.
4. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that the complex hazardous waste materials containing lead and antimony are hazardous waste materials containing 25% lead, 8% antimony and 1% tin.
5. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that the complex hazardous waste materials containing lead and antimony are hazardous waste materials containing 20% lead, 5% antimony and 1% tin.
6. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that the side blowing reduction furnace is an 8.4 m? side blowing reduction furnace.
7. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that the capacity of the stainless steel anode pot is 1 m3.
8. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that in step (4), the lead-antimony alloy anode plate contains 82% Pb, 16% Sb and 0.2% Cu, and the lead-antimony alloy anode plate is put into a lead electrolytic cell for electrolysis, each lead-antimony alloy anode plate weighs 90 Kg, and each cell contains 35 pieces, the current density is 150 A/m?, and the electrolyte composition is: H2SiFs (total) 115.08 g/L, Pb?* 42.77 g/L, H:SiF6 (swim) 85.33 g/L, electrifying time: 70 h, the precipitated lead meets the national standard of 0# refined lead, and the anode mud contains 15% pH 207666 62% Sb and 1.5% Cu.
9. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that in step (4), the lead-antimony alloy anode plate contains 82% Pb, 16% Sb and 0.2% Cu, and the lead-antimony alloy anode plate is put into a lead electrolytic cell for electrolysis, each lead-antimony alloy anode plate weighs 90 Kg, each cell contains 35 pieces, the current density is 150 A/m?, and the electrolyte composition is: HzSiFs (total) 112.08 g/L, Pb”
45.71 g/L, H:SiF6 (swim) 88.23 g/L, electrifying time: 70 h, the precipitated lead meets the national standard of 0# refined lead, and the anode mud contains 12% Pb, 65% Sb and 1.8% Cu.
10. The method for recovering lead, antimony and tin from antimony-lead-containing complex hazardous waste materials according to claim 1, characterized in that in step (4), the lead-antimony alloy anode plate contains 82% of Pb, 16% of Sb and 0.2% of Cu, and the lead-antimony alloy anode plate is put into a lead electrolytic cell for electrolysis, each lead-antimony alloy anode plate weighs 90 Kg, each cell contains 35 pieces, the current density is 145 A/m?, and the electrolyte composition is: H2SiFs (total) 118.18 g/L, Pb?" 46.87 g/L, H:SiF6 (swim) 88.37 g/L, electrifying time: 65 h, the precipitated lead meets the national standard of 0# refined lead, and the anode mud contains 12.1% Pb,
66.4% Sb and 1.7% Cu.
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| CN202211615234.8A CN115821053A (en) | 2022-12-15 | 2022-12-15 | A method for recovering lead, antimony and tin from complex lead and antimony hazardous waste materials |
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| GB253908A (en) * | 1925-06-17 | 1927-09-14 | Max Speichert | A process for treating lead-tin alloys derived from waste material from lead smelting works |
| RU2154682C1 (en) * | 1999-04-21 | 2000-08-20 | Институт металлургии Уральского отделения РАН | Method of recovery of non-ferrous metals from copper-and-lead wastes containing tin and antimony |
| CN101532091B (en) * | 2009-04-17 | 2010-12-29 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Technology of extracting and separating valuable metals such as Pb, In, Sb, Cu and Sn from lead smelting converter slags |
| CN101705372B (en) * | 2009-11-25 | 2011-09-21 | 郴州市金贵银业股份有限公司 | Process for extracting tin from wet lead with high tin content |
| CN104120445A (en) * | 2014-07-28 | 2014-10-29 | 蒙自矿冶有限责任公司 | Electrolytic method of high-antimony lead |
| CN107354299B (en) * | 2017-05-23 | 2019-05-17 | 甘肃中色东方工贸有限公司 | The recoverying and utilizing method of Cu, Pb, Zn, Fe in metal smelt process slag |
| CN107312935A (en) * | 2017-06-30 | 2017-11-03 | 郴州市金贵银业股份有限公司 | A kind of processing method of reducing slag after lead anode slurry melting |
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| WO2024124684A1 (en) | 2024-06-20 |
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