CN114540631B - Method for smelting copper dross and recovering valuable metal - Google Patents
Method for smelting copper dross and recovering valuable metal Download PDFInfo
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- CN114540631B CN114540631B CN202210108883.2A CN202210108883A CN114540631B CN 114540631 B CN114540631 B CN 114540631B CN 202210108883 A CN202210108883 A CN 202210108883A CN 114540631 B CN114540631 B CN 114540631B
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- 239000010949 copper Substances 0.000 title claims abstract description 161
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 160
- 238000003723 Smelting Methods 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 109
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 239000002893 slag Substances 0.000 claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052718 tin Inorganic materials 0.000 claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003546 flue gas Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000004615 ingredient Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004071 soot Substances 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 26
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011133 lead Substances 0.000 description 88
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 238000011084 recovery Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- -1 copper metals Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—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
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- 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
- 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
- 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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- 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 method for smelting copper dross and recovering valuable metals. Copper scum, scrap iron, slag forming agent and reducing agent are used as raw materials for batching; adding the prepared materials into a smelting furnace for heating reduction smelting, and generating crude lead, smelting slag, matte and flue gas through reduction smelting; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte; the generated lead bullion enters a tin removal process, and after tin making slag, the lead bullion enters a lead bullion electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients. According to the technical scheme, the fluidity of the copper dross smelting slag can be obviously improved, the layering effect of slag, matte and crude lead in the furnace in the smelting process is enhanced, the phenomena of slag generation and material collapse in the furnace are reduced, the slag index is obviously reduced, the operation is safe and controllable, and the labor intensity is reduced.
Description
1. Technical field:
the invention belongs to the nonferrous metal pyrometallurgy industry, and particularly relates to a method for smelting copper dross and recovering valuable metals.
2. The background technology is as follows:
copper dross is a product of the fire refining and liquation of crude lead, which accounts for about 2% of the crude lead content, and mainly consists of copper sulfide, lead oxide and metallic lead, and also contains tin, arsenic, zinc, cadmium, silver, gold and other metallic elements. The copper dross forms and components have larger differences due to different slag dragging modes or slag dragging equipment. The copper dross contains abundant valuable metals, generally contains 2-40% of copper, 40-85% of lead, 300-1000 g/t of silver and 20-100 g/t of gold. Therefore, if the copper dross is not comprehensively utilized, secondary resource waste is caused; meanwhile, elements such as lead, arsenic, cadmium and the like in the copper dross also cause serious pollution to the environment.
At present, most domestic lead smelting enterprises adopt a pyrogenic process to recycle valuable metals such as lead, copper, silver and the like in copper dross. The pyrogenic process copper dross can be classified into a reverberatory furnace smelting method, a blast furnace smelting method, a rotary kiln smelting method, an electric furnace smelting method, a side-blown furnace smelting method, a bottom-blown furnace smelting method, a top-blown furnace smelting method, a vacuum metallurgical method, and the like, depending on the processing equipment. The process for treating copper dross by using the reverberatory furnace is the most commonly used process at present, and most of domestic lead smelting enterprises adopt the process to treat copper dross, but the process has high energy consumption, serious environmental pollution, short service life of the furnace and the like, and is classified as a limited-period process by China. The process for treating copper dross by adopting a blast furnace has the defects of incomplete copper and lead separation and low copper matte yield. The rotary kiln is adopted to treat copper dross, so that the problems of high oil consumption and high cost exist. The electric furnace method is difficult to realize in areas with shortage of electric power, and the electric furnace method also needs to add reducing agent coke, so that the production cost is high. The methods such as a side-blowing furnace smelting method, a bottom-blowing furnace smelting method, a top-blowing furnace smelting method and the like are not put into industrial production; vacuum metallurgy is still in the test stage at present, and many problems of large-scale production are not solved.
Currently, in the patent and literature on the pyrogenic treatment of copper dross, the traditional soda-iron filings process is mostly used. The purpose of adding the soda in the treatment process is to reduce the melting points of slag and matte to form sodium matte, reduce lead in the matte and slag, lead arsenic and antimony to form sodium salt for slagging, and remove part of arsenic and antimony; the scrap iron has the function of reducing PbS in copper dross into metallic lead and enriching copper in copper matte; coke is added to maintain a certain reducing atmosphere in the furnace to prevent oxidation of sulfides, so as to ensure enough sulfur for sulfonium production and the reduction of PbO, and gold and silver are enriched by lead bullion. The method has the advantages of high lead recovery rate and low lead content in the lead matte. The technological process of treating copper dross by a fire method is short, easy to implement and low in cost, but the corrosiveness of molten salt is increased at high temperature due to the addition of soda and scrap iron, the corrosion and the intersection of furnace lining are serious, the service life of a smelting furnace is greatly shortened, and new impurities are brought to the subsequent copper extraction process by the addition of the two substances, so that the treatment difficulty and the treatment cost are increased. In addition, the method has the disadvantages of low copper recovery rate, high yield of white matte, general 3-5% of lead in slag and general 2-3% of copper in slag, high content of valuable metals and the like. Tin metal in the copper dross is dispersed into ash and waste slag, so that the tin content of the crude lead is less than 0.05 percent.
The wet process is used for treating copper dross, which is divided into an acid leaching method, an ammonia leaching method and an alkaline leaching method according to different methods, and the wet process of the copper dross can well separate lead and copper. The wet process for treating copper dross has the advantages of high copper-lead separation degree, complex process, high corrosion resistance requirement, high equipment investment, high cost, high heavy metal content in waste liquid and the like. Therefore, in order to better utilize resources, improve environment, save energy, improve production efficiency and reduce production cost, a new process for treating copper dross has been developed.
3. The invention comprises the following steps:
the invention aims to solve the technical problems that: according to the problems existing in the existing recovery processing technology of copper dross at present, the invention provides a method for efficiently smelting and separating lead copper tin valuable metals from copper dross, namely the invention provides a novel method for smelting and recovering valuable metals from copper dross. According to the invention, the slag former is adopted to replace sodium carbonate, so that the fluidity of smelting slag is greatly improved, and the lead content and copper content of slag are obviously reduced. By adding the reducing agent to form a reducing atmosphere, arsenic and antimony in the copper dross are reduced into the ash, and white matte is not basically formed. Meanwhile, under the reducing atmosphere, the simple substance form of the reduced tin metal in the copper dross enters the lead bullion, and the lead bullion produces tin dross in the subsequent tin dross production process.
In order to solve the problems, the invention adopts the following technical scheme:
the invention provides a method for smelting copper dross and recovering valuable metals, which comprises the following steps:
a. taking copper dross, scrap iron, a slag former and a reducing agent as raw materials, wherein the addition of the scrap iron is 2-7% of the total weight of the copper dross, the addition of the slag former is 2-10% of the total weight of the copper dross, and the addition of the reducing agent is 1-10% of the total weight of the copper dross;
b. b, proportioning according to the dosage of the step a, adding the prepared material into a smelting furnace for heating reduction smelting, wherein the smelting temperature is controlled to 1150-1250 ℃ in the smelting process, and the smelting time is 12h;
c. reducing and smelting to produce crude lead, smelting slag, matte and flue gas; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte;
d. c, the crude lead generated in the step c enters a tin removal process, and after tin making slag, the crude lead enters a crude lead electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients.
According to the method for smelting and recovering valuable metals from copper dross, the copper dross in the step a is generated in the lead bullion copper removal process.
According to the method for smelting and recovering valuable metals from the copper dross, in the step a, the copper dross contains 50-70% by mass of lead, 5-30% by mass of copper, 3-10% by mass of antimony, 1-5% by mass of sulfur, less than or equal to 1.5% by mass of tin and less than or equal to 1% by mass of iron.
According to the method for smelting and recovering valuable metals from copper dross, the slag former is antimony smelting slag, and the reducing agent is carbon particles.
According to the method for smelting and recovering valuable metals from copper dross, na in the antimony smelting slag 2 The mass percentage of O is 40-60 percent, siO 2 The mass percentage is 5-15 percent, fe 2 O 3 The mass percentage is 5-10%、Al 2 O 3 The mass percentage is 3-10%, and the mass percentage of CaO is less than or equal to 5%.
According to the method for smelting and recovering valuable metals from copper dross, the granularity of the carbon particles is 3-5 mm; the carbon particles contain 70-75% of fixed carbon by mass, 10-15% of volatile components by mass, 5-10% of ash by mass and less than or equal to 0.5% of S by mass.
According to the method for smelting and recovering valuable metals from copper dross, in the step a, the addition amount of scrap iron is 3% of the total weight of the copper dross, the addition amount of the slag former is 7% of the total weight of the copper dross, and the addition amount of the reducing agent is 4% of the total weight of the copper dross.
According to the method for smelting and recycling valuable metals from copper dross, the content of lead in the smelting slag obtained in the step c is less than 1% by mass, and the content of copper in the smelting slag is less than 1.5% by mass.
According to the method for smelting and recovering valuable metals from copper dross, the mass percentage of tin in the crude lead obtained in the step c is more than 0.4%.
The invention adopts the combination of antimony smelting slag and carbon particles to replace sodium carbonate slagging and form reducing atmosphere to realize the high-efficiency separation of valuable metals of lead, copper and tin in copper dross smelting, and the principle is as follows:
the smelting temperature of the antimony slag alkaline smelting process is 900-950 ℃, under the temperature condition, the antimony smelting slag has higher fluidity, the smelting temperature of the copper dross is 1150-1250 ℃, and under the temperature condition, when a large amount of sodium antimonate exists in the antimony smelting slag and is matched with the copper dross for smelting, the produced slag has better fluidity. The slag has better fluidity, and the precipitation separation effect of the lead bullion and the copper matte is obviously improved. The antimony smelting slag is used as waste slag to replace sodium carbonate, so that the slag fluidity is improved, and the secondary utilization of resources is realized. The addition of carbon particles ensures that the smelting process of copper dross maintains stronger reducibility, and tin in the copper dross can be reduced into lead bullion to reach the standard of 0.4 percent of tin required by lead bullion tin extraction. When the traditional soda scrap iron method is used for proportioning, the proportion of soda is generally 7-8%, the proportion of scrap iron is 6-7%, the content of lead and copper in slag is higher, and the smelting cost is higher. In addition, when no carbon particles are added, tin in the copper dross mainly volatilizes into smoke dust and remains in the dross, and cannot be effectively recovered.
The invention has the positive beneficial effects that:
1. according to the technical scheme, the antimony smelting slag is used for replacing sodium carbonate as a slag former, so that the high-efficiency separation of lead and copper metals in the copper dross smelting slag is ensured, and the indexes of lead and copper in the slag are obviously improved. The use of sodium carbonate is eliminated, the smelting cost of copper dross is reduced by 50-60%, and the smelting economy is greatly improved. Therefore, the invention has remarkable economic benefit.
2. According to the technical scheme, carbon particles are adopted as a reducing agent to be mixed into copper dross, the reducing atmosphere in the smelting process is enhanced, tin in the copper dross can be reduced into lead bullion, the lead bullion produces tin dross in a tin removal process, and valuable tin metal is recovered.
3. According to the technical scheme, the fluidity of the copper dross smelting slag can be obviously improved, the layering effect of slag, matte and crude lead in the furnace in the smelting process is enhanced, the phenomena of slag generation and material collapse in the furnace are reduced, the slag index is obviously reduced, the operation is safe and controllable, and the labor intensity is reduced.
5. In the technical scheme of the invention, sodium carbonate is not used as a slag former, and compared with the traditional sodium carbonate scrap iron method, the method has the advantages of reduced auxiliary material input proportion, reduced slag yield and reduced industrial solid waste production.
6. According to the technical scheme, the antimony smelting slag is industrial solid waste generated by other furnaces, and after being used as a slag former, the antimony smelting slag is converted into available resources from the industrial waste, so that the secondary utilization of the industrial solid waste is realized.
In conclusion, the invention has remarkable economic and social benefits.
4. Description of the drawings:
FIG. 1 is a schematic diagram of the process flow of the method for smelting and recovering valuable metals from copper dross in the invention.
5. The specific embodiment is as follows:
the invention is further illustrated in the following figures and examples, which are not intended to limit the scope of the technical solution of the invention.
Copper dross adopted in the following examples of the present invention is produced in the lead bullion process; the mass percentage of each element in the copper dross is shown in table 1.
TABLE 1 copper dross contains the elements in mass percent
| Element(s) | Pb％ | Cu％ | Sn％ | Fe％ | S％ | Sb％ |
| Content of | 66.93 | 15.23 | 0.75 | 0.32 | 2.4 | 4.4 |
In the technical scheme of the invention, the adopted slag former is antimony smelting slag produced by alkaline smelting of antimony slag, and the main components and the percentage content thereof are shown in Table 2 in detail.
TABLE 2 main components and contents of antimony smelting slag as slag former of the present invention
| Composition of the components | Na 2 O％ | SiO 2 ％ | Fe 2 O 3 ％ | Al 2 O 3 ％ | CaO％ |
| Content of | 52.89 | 13.5 | 7.61 | 4.64 | 2.08 |
In the technical scheme of the invention, the main components and the contents of the main components in the reducer carbon particles are shown in Table 3.
TABLE 3 major Components and contents of the reducing agent carbon particles of the invention
| Particle size mm | Fixed carbon% | Volatile matter% | Ash% | Sulfur content% |
| 3～5mm | 73.37 | 14.24 | 9.36 | 0.39 |
Comparative example 1: the traditional copper dross sodium carbonate scrap iron method treatment method comprises the following detailed steps:
a. copper scum, scrap iron and sodium carbonate produced in the copper removing process of crude lead are used for batching; the addition of the scrap iron is 6-7% of the total weight of the copper dross, and the addition of the sodium carbonate is 6-7% of the total weight of the copper dross;
b. adding the prepared materials into a copper dross smelting furnace for heating reduction smelting, and controlling the smelting temperature to 1150-1250 ℃ in the smelting process;
c. the reduction smelting reaction takes 12 hours as a furnace period, and the operations of lead bullion, copper matte and slag are carried out once in the period; under the condition of reducing atmosphere, lead metal in copper dross mainly enters crude lead, tin metal mainly enters crude lead, and copper metal mainly enters copper matte; the mass percentage of tin in the obtained crude lead is 0.02 percent; the obtained smelting slag contains 4.95 mass percent of lead and 2.65 mass percent of copper;
d. the crude lead produced in the copper dross reduction smelting process enters a next tin removal process, and after tin slag is produced, the crude lead enters a crude lead electrolysis process to produce electrolytic lead;
e. matte produced in the copper dross reduction smelting process enters a converting process to produce blister copper.
Example 1:
the invention relates to a method for smelting and recycling valuable metals from copper dross, which comprises the following detailed steps:
a. taking copper dross, scrap iron, slag former antimony smelting slag and reducing agent carbon particles as raw materials, wherein the addition amount of the scrap iron is 3% of the total weight of the copper dross, the addition amount of the slag former antimony smelting slag is 7% of the total weight of the copper dross, and the addition amount of the reducing agent carbon particles is 4% of the total weight of the copper dross;
b. b, burdening according to the dosage of the step a, adding the formulated material into a smelting furnace for heating reduction smelting, wherein the smelting temperature is controlled to be 1200 ℃ in the smelting process, and the smelting time is 12 hours;
c. reducing and smelting to produce crude lead, smelting slag, matte and flue gas; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte; the mass percentage of tin in the obtained crude lead is 0.57%; the obtained smelting slag contains 0.78 percent of lead by mass and 1.36 percent of copper by mass;
d. c, the crude lead generated in the step c enters a tin removal process, and after tin making slag, the crude lead enters a crude lead electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients.
Example 2:
the invention relates to a method for smelting and recycling valuable metals from copper dross, which comprises the following detailed steps:
a. taking copper dross, scrap iron, slag former antimony smelting slag and reducing agent carbon particles as raw materials, wherein the addition amount of the scrap iron is 3% of the total weight of the copper dross, the addition amount of the slag former antimony smelting slag is 6% of the total weight of the copper dross, and the addition amount of the reducing agent carbon particles is 4% of the total weight of the copper dross;
b. b, burdening according to the dosage of the step a, adding the formulated material into a smelting furnace for heating reduction smelting, wherein the smelting temperature is controlled to 1150 ℃ in the smelting process, and the smelting time is 12 hours;
c. reducing and smelting to produce crude lead, smelting slag, matte and flue gas; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte; the mass percentage of tin in the obtained crude lead is 0.69%; the obtained smelting slag contains 0.81 percent of lead by mass and 1.24 percent of copper by mass;
d. c, the crude lead generated in the step c enters a tin removal process, and after tin making slag, the crude lead enters a crude lead electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients.
Example 3:
the invention relates to a method for smelting and recycling valuable metals from copper dross, which comprises the following detailed steps:
a. taking copper dross, scrap iron, slag former antimony smelting slag and reducing agent carbon particles as raw materials, wherein the addition amount of the scrap iron is 3% of the total weight of the copper dross, the addition amount of the slag former antimony smelting slag is 8% of the total weight of the copper dross, and the addition amount of the reducing agent carbon particles is 4% of the total weight of the copper dross;
b. b, burdening according to the dosage of the step a, adding the formulated material into a smelting furnace for heating reduction smelting, wherein the smelting temperature is controlled to 1250 ℃ in the smelting process, and the smelting time is 12 hours;
c. reducing and smelting to produce crude lead, smelting slag, matte and flue gas; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte; the mass percentage of tin in the obtained crude lead is 0.65%; the obtained smelting slag contains 0.79 percent of lead by mass and 1.17 percent of copper by mass;
d. c, the crude lead generated in the step c enters a tin removal process, and after tin making slag, the crude lead enters a crude lead electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients.
Compared with the traditional copper dross treatment process, the technical scheme provided by the invention has the relevant performance index comparison condition shown in Table 4.
Table 4 comparative example 1 and inventive examples 1-3 comparative cases of copper dross treatment
As can be seen from the comparison, the copper dross smelting is treated by adopting the technical scheme of the invention, the lead recovery rate can reach 98 percent, and the copper recovery rate can reach 93 percent; the traditional soda scrap iron process is adopted for treatment, the lead recovery rate is 96%, and the copper recovery rate is 85%. By adopting the technical scheme of the invention, the scrap iron is reduced and sodium carbonate is not added for slagging, so that the smelting cost of the lead bullion is obviously reduced, the tin content of the lead bullion is obviously increased, and the requirements of the downstream process for producing the tin slag from the lead bullion are met. Therefore, the invention can improve and reduce lead and copper in slag, so as to improve the recovery rate of lead and copper, reduce the cost of auxiliary materials, recover valuable metal tin in copper dross, and have higher economic and social benefits.
Claims (5)
1. A method for smelting copper dross and recovering valuable metals, the method comprising the steps of:
a. taking copper dross, scrap iron, a slag former and a reducing agent as raw materials, wherein the addition of the scrap iron is 2-7% of the total weight of the copper dross, the addition of the slag former is 2-10% of the total weight of the copper dross, and the addition of the reducing agent is 1-10% of the total weight of the copper dross;
the slag former is antimony smelting slag, and the reducing agent is carbon particles; na in the antimony smelting slag 2 The mass percentage of O is 40-60 percent, siO 2 The mass percentage is 5-15 percent, fe 2 O 3 The mass percentage is 5-10 percent, al 2 O 3 3-10% by mass and less than or equal to 5% by mass of CaO; the granularity of the carbon particles is 3-5 mm; the carbon particles comprise 70-75% of fixed carbon, 10-15% of volatile matter, 5-10% of ash and less than or equal to 0.5% of S;
b. b, proportioning according to the dosage of the step a, adding the prepared material into a smelting furnace for heating reduction smelting, wherein the smelting temperature is controlled to 1150-1250 ℃ in the smelting process, and the smelting time is 12h;
c. reducing and smelting to produce crude lead, smelting slag, matte and flue gas; lead metal in copper dross enters lead bullion, tin metal enters lead bullion, and copper metal enters copper matte;
d. c, the crude lead generated in the step c enters a tin removal process, and after tin making slag, the crude lead enters a crude lead electrolysis process to produce electrolytic lead; transferring matte into a copper smelting system for recycling; the flue gas is subjected to dust collection treatment, the flue gas obtained after the treatment enters a tail gas system for evacuation, and the obtained soot returns to a smelting process to be reused as ingredients.
2. The method for recovering valuable metals by smelting copper dross according to claim 1, wherein: the copper dross in step a is generated in the lead bullion process.
3. The method for recovering valuable metals by smelting copper dross according to claim 1, wherein: the copper dross in the step a contains 50 to 70 percent of lead, 5 to 30 percent of copper, 3 to 10 percent of antimony, 1 to 5 percent of sulfur, less than or equal to 1.5 percent of tin and less than or equal to 1 percent of iron.
4. The method for recovering valuable metals by smelting copper dross according to claim 1, wherein: the adding amount of the scrap iron in the step a is 3% of the total weight of the copper dross, the adding amount of the slag former is 7% of the total weight of the copper dross, and the adding amount of the reducing agent is 4% of the total weight of the copper dross.
5. The method for recovering valuable metals by smelting copper dross according to claim 1, wherein: and c, the smelting slag obtained in the step c contains less than 1% by mass of lead and less than 1.5% by mass of copper.
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