CN112708766A - Method for recovering valuable metals in copper-containing electronic waste - Google Patents
Method for recovering valuable metals in copper-containing electronic waste Download PDFInfo
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- CN112708766A CN112708766A CN202011490908.7A CN202011490908A CN112708766A CN 112708766 A CN112708766 A CN 112708766A CN 202011490908 A CN202011490908 A CN 202011490908A CN 112708766 A CN112708766 A CN 112708766A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000010949 copper Substances 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- 239000010793 electronic waste Substances 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000002739 metals Chemical class 0.000 title claims abstract description 22
- 238000000197 pyrolysis Methods 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000003723 Smelting Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000779 smoke Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000007664 blowing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 235000019738 Limestone Nutrition 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000006028 limestone Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000010792 electronic scrap Substances 0.000 claims 6
- 230000004907 flux Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 239000010931 gold Substances 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000428 dust Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
-
- 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
- C22B15/003—Bath 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- C22B15/0056—Scrap treating
-
- 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
-
- 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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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention relates to a method for recovering valuable metals from copper-containing electronic waste, belonging to the technical field of dangerous solid waste smelting and resource comprehensive utilization. The method comprises the steps of crushing copper-containing electronic waste into particles with the particle size of 20-30mm to obtain copper-containing electronic waste particles, carrying out anaerobic pyrolysis on the copper-containing electronic waste particles to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil, and uniformly mixing the pyrolysis solid residues, copper residues and a fluxing agent to obtain a mixed material; adding the mixed material into an oxygen-enriched top-blown converter for oxygen-enriched smelting, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining on the blister copper to obtain anode mud, and emptying the smelting smoke after cooling, dedusting, activated carbon adsorption and alkali liquor absorption in sequence. The method effectively recovers valuable components of copper, gold and silver of the copper-containing electronic waste, obtains the crude copper rich in precious metals, realizes the enrichment and recovery of the valuable metals, can use the slag as a building material, and realizes the comprehensive utilization of the copper-containing electronic waste and the copper slag.
Description
Technical Field
The invention relates to a method for recovering valuable metals from copper-containing electronic waste, belonging to the technical field of dangerous solid waste smelting and resource comprehensive utilization.
Background
The electronic waste has the characteristics of high yield, high content of valuable metals, high harmfulness and the like, so that the electronic waste becomes non-common garbage, and the most appropriate treatment mode must be found so as to achieve the highest economic and environmental benefits. The recycling of electronic waste has become a major issue worldwide.
The pyrometallurgical technology is a traditional method for recovering metals, and the pyrometallurgical treatment comprises incineration, smelting, sintering, melting and the like, and the main purpose of the pyrometallurgical technology is to separate metal substances and non-metal substances in copper-containing electronic waste materials, wherein one part of the non-metal substances can become a gas escape system, and the other part of the non-metal substances floats on the upper layer of a metal molten material in the form of scum, so that the metal and the non-metal materials are separated, and the metal is oxidized into metal oxides in oxygen.
However, in the prior art, the recovery process flow of valuable metals in the electronic waste is long, and a slagging agent needs to be added during smelting, so that the cost and the slag amount are increased. Therefore, a valuable metal recovery method with short process flow and less slag is urgently needed.
Disclosure of Invention
The invention provides a method for recovering valuable metals from copper-containing electronic waste, which aims at solving the problems of low recovery rate and high cost of the valuable metals in the copper-containing electronic waste in the prior art.
A method for recovering valuable metals from copper-containing electronic waste comprises the following specific steps:
(1) crushing the copper-containing electronic waste to obtain copper-containing electronic waste particles with the particle size of 20-30 mm;
(2) carrying out anaerobic pyrolysis on the copper-containing electronic waste particles obtained in the step (1) to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil;
(3) uniformly mixing the pyrolysis solid residue, the copper slag and the fluxing agent in the step (2) to obtain a mixed material;
(4) adding the mixed material into an oxygen-enriched top-blown converter for smelting, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining on the blister copper to obtain anode mud, and emptying the smelting smoke after cooling, dedusting, activated carbon adsorption and alkali liquor absorption in sequence; adsorbing with activated carbon to obtain smoke dust;
the copper-containing electronic waste material in the step (1) comprises one or more of leftover materials for producing circuit boards, waste mobile phones, waste computers, waste keyboards and waste circuit boards;
the anaerobic pyrolysis temperature in the step (2) is 400-700 ℃;
the pyrolysis solid residue in the step (2) contains a mixture of carbon, silicon dioxide and metal, and in mass percent, C10-15% and SiO in the pyrolysis solid residue220～30％、Cu15～50％、Sn2～4％、Pb1～2％、Zn2～3％，Au20～200g/t，Ag200～500g/t；
The fluxing agent in the step (3) comprises pure CaO, limestone or a substance containing CaO;
further, the copper slag in the step (3) contains 2-4% of Cu, 35-45% of TFe and SiO220～35％、CaO 1～5％；
Based on 100% of the mass of the mixed material, the copper slag in the step (3) accounts for 35% -40%, the fluxing agent accounts for 5-10%, and the balance is pyrolytic solid residues;
the temperature of the oxygen-enriched top-blown smelting in the step (4) is 1250-1400 ℃, and the oxygen-enriched concentration is 40-70%; the content of copper, gold and silver in the crude copper produced by smelting is respectively 90-95%, 30-400 g/t and A in percentage by massg, 300-600 g/t, wherein the contents of tin, lead and zinc in the produced smoke dust are 5-10%, 10-20% and Zn 20-40% respectively; 0.5-1.0% of Fe/Si in the slag, 15-18% of CaO, and Al2O3The content is 10-16%, and the copper content of the slag is less than or equal to 1%; the slag can be used as building materials by furnace cooling or water quenching;
the concentration of dioxin in the flue gas is lower than 0.5ngTEQ/m3。
The invention has the beneficial effects that:
(1) the method takes the copper slag as the raw material of the slagging constituent copper for oxygen-enriched smelting, and realizes the comprehensive recovery of the copper slag and the pyrolysis solid residue;
(2) the method adopts anaerobic pyrolysis to ensure that carbon in the pyrolysis solid residue is not oxidized into carbon dioxide or carbon monoxide, so that the carbon is kept in the pyrolysis solid residue as much as possible, the glass fiber is prevented from being excessively oxidized by adopting the anaerobic pyrolysis, and the glass fiber component and the carbon in the pyrolysis solid residue can be used as a slagging agent and a reducing agent for oxygen-enriched smelting;
(3) the carbon generated by the anaerobic pyrolysis of the method can partially reduce the metal oxide into simple substances in the anaerobic pyrolysis process;
(4) the concentration of dioxin in the flue gas is lower than 0.5ngTEQ/m3The recovery rate of valuable metals in the whole process is high, and the method is environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for recovering valuable metals in copper-containing electronic waste (see figure 1) comprises the following specific steps:
(1) crushing the copper-containing electronic waste to obtain copper-containing electronic waste particles with the particle size of 20-30 mm;
(2) carrying out anaerobic pyrolysis on copper-containing electronic waste particles at the temperature of 500 ℃ to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil; wherein the pyrolysis solid residue contains carbon and silicon dioxideAnd a metal mixture, wherein the mass percent of the C10 percent and the SiO are obtained in the pyrolysis solid residue230％、Cu30％、Sn2％、Pb1.2％、Zn2.3％，Au30 g/t，Ag200g/t；
(3) Uniformly mixing the pyrolysis solid residue, the copper slag and the fluxing agent (limestone) in the step (2) to obtain a mixed material; wherein, the copper slag contains 4.06 percent of Cu, 39.98 percent of TFe and SiO in percentage by mass225.10 percent of CaO and 2.29 percent of CaO; the mass content of CaO in the limestone is 70 percent; based on 100% of the mass of the mixed material, the copper slag accounts for 40%, the fluxing agent (limestone) accounts for 10%, and the pyrolysis solid residue accounts for 50%;
(4) adding the mixed material obtained in the step (3) into an oxygen-enriched top-blowing furnace, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air, carrying out oxygen-enriched top-blowing smelting at the temperature of 1250 ℃ and the oxygen-enriched concentration of 40% to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining and purification on the blister copper to obtain anode mud, and collecting the smelting smoke by using a gas collecting bag after cooling, dedusting, active carbon adsorption and alkali liquor absorption in sequence; adsorbing with activated carbon to obtain smoke dust; wherein the contents of copper, gold and silver in the crude copper produced by smelting are respectively 92%, 40g/t and 300 g/t; the content of Fe/Si in the slag is 0.55, the content of CaO is 15 percent, and Al2O3The content is 15.5 percent, and the content of copper is 0.8 percent; the contents of tin, lead and tin in the produced smoke dust are respectively 5%, 10% and 20%;
ICP analysis showed that the dioxin content in the gas collected in the gas collection bag of this example was 0.2ng TEQ/m3。
Example 2: a method for recovering valuable metals in copper-containing electronic waste (see figure 1) comprises the following specific steps:
(1) crushing the copper-containing electronic waste to obtain copper-containing electronic waste particles with the particle size of 20-30 mm;
(2) carrying out anaerobic pyrolysis on copper-containing electronic waste particles at the temperature of 600 ℃ to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil; wherein the pyrolysis solid residue contains carbon, silicon dioxide and metal mixture, and the pyrolysis solid residue contains C12% and SiO in percentage by mass230％、Cu40％、Sn2.8％、Pb1.5％、Zn2.4％，Au35g/t，Ag240g/t；
(3) Uniformly mixing the pyrolysis solid residue, the copper slag and the fluxing agent (limestone) in the step (2) to obtain a mixed material; wherein, the copper slag contains, by mass percent, Cu3.16%, TFe40.07%, SiO223.36 percent and CaO3.14 percent; the mass content of CaO in the limestone is 98 percent; based on the mass of the mixed material as 100%, the copper slag accounts for 35%, the fluxing agent (limestone) accounts for 10%, and the pyrolysis solid residue accounts for 55%;
(4) adding the mixed material obtained in the step (3) into an oxygen-enriched top-blowing furnace, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air, carrying out oxygen-enriched top-blowing smelting at the temperature of 1300 ℃ and the oxygen-enriched concentration of 55% to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining on the blister copper to obtain anode mud, and collecting the smelting smoke by using a gas collecting bag after cooling, dedusting, active carbon adsorption and alkali liquor absorption in sequence; adsorbing with activated carbon to obtain smoke dust; wherein the copper, gold and silver contents in the crude copper produced by smelting are respectively 94%, 55g/t and 450 g/t; the slag contains Fe/Si of 0.63, CaO of 17%, and Al2O3The content is 16 percent, and the content of copper is 0.6 percent; the contents of tin, lead and tin in the produced smoke are respectively 8%, 12% and 23%;
ICP analysis showed that the dioxin content in the gas collected in the gas collection bag of this example was 0.15ng TEQ/m3。
Example 3: a method for recovering valuable metals in copper-containing electronic waste (see figure 1) comprises the following specific steps:
(1) crushing the copper-containing electronic waste to obtain copper-containing electronic waste particles with the particle size of 20-30 mm;
(2) carrying out anaerobic pyrolysis on copper-containing electronic waste particles at the temperature of 700 ℃ to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil; wherein the pyrolysis solid residue contains carbon, silicon dioxide and metal mixture, and the pyrolysis solid residue contains C15% and SiO in percentage by mass235％、Cu40％、Sn3％、Pb1.8％、Zn2.6％，Au50g/t，Ag310g/t；
(3) Uniformly mixing the pyrolysis solid residue, the copper slag and the fluxing agent (limestone) in the step (2) to obtain a mixed material; wherein, the weight percentage of the components is,the copper slag contains Cu3.82%, TFe38.80%, and SiO225.00 percent and CaO2.84 percent; the mass content of CaO in the limestone is 58 percent; based on the mass of the mixed material as 100%, the copper slag accounts for 35%, the fluxing agent (limestone) accounts for 5%, and the pyrolysis solid residue accounts for 60%;
(4) adding the mixed material obtained in the step (3) into an oxygen-enriched top-blowing furnace, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air, carrying out oxygen-enriched top-blowing smelting at the temperature of 1350 ℃ and the oxygen-enriched concentration of 70% to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining on the blister copper to obtain anode mud, and collecting the smelting smoke by using a gas collecting bag after cooling, dedusting, activated carbon adsorption and alkali liquor absorption in sequence; adsorbing with activated carbon to obtain smoke dust; wherein the content of copper, gold and silver in the crude copper produced by smelting is respectively 95%, 64g/t and 500 g/t; the content of Fe/Si in the slag is 0.84 percent, the content of CaO is 18 percent, and Al is contained2O3The content is 14 percent, and the content of copper is 0.6 percent; the contents of tin, lead and zinc in the produced smoke dust are respectively 7%, 11% and 21%;
ICP analysis showed that the dioxin content in the gas collected in the gas collecting bag of this example was 0.10ng TEQ/m3。
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (7)
1. A method for recovering valuable metals from copper-containing electronic waste is characterized by comprising the following specific steps:
(1) crushing the copper-containing electronic waste to obtain copper-containing electronic waste particles with the particle size of 20-30 mm;
(2) carrying out anaerobic pyrolysis on the copper-containing electronic waste particles obtained in the step (1) to obtain pyrolysis gas, pyrolysis solid residues and pyrolysis oil;
(3) uniformly mixing the pyrolysis solid residue, the copper slag and the fluxing agent in the step (2) to obtain a mixed material;
(4) and (3) adding the mixed material obtained in the step (3) into an oxygen-enriched top-blown converter for oxygen-enriched smelting, simultaneously blowing oxygen-enriched air and controlling the concentration of the oxygen-enriched air to obtain smelting smoke, blister copper and furnace slag, carrying out electrolytic refining on the blister copper to obtain anode mud, and emptying the smelting smoke after cooling, dedusting, activated carbon adsorption and alkali liquor absorption in sequence.
2. The method for recovering valuable metals from copper-containing electronic scrap as claimed in claim 1, wherein: the copper-containing electronic waste in the step (1) comprises one or more of leftover materials for producing circuit boards, waste mobile phones, waste computers, waste keyboards and waste circuit boards.
3. The method for recovering valuable metals from copper-containing electronic scrap as claimed in claim 1, wherein: and (3) the anaerobic pyrolysis temperature in the step (2) is 400-700 ℃.
4. The method for recovering valuable metals from copper-containing electronic scrap according to claim 1 or 3, wherein: the pyrolysis solid residue in the step (2) contains a mixture of carbon, silicon dioxide and metal, wherein in mass percent, C10-15%, SiO are contained in the pyrolysis solid residue220～30％、Cu15～50％、Sn2～4％、Pb1～2％、Zn2～3％，Au20～200g/t，Ag200～500g/t。
5. The method for recovering valuable metals from copper-containing electronic scrap as claimed in claim 1, wherein: the flux in the step (3) comprises pure CaO, limestone or a substance containing CaO.
6. The method for recovering valuable metals from copper-containing electronic scrap according to claim 1 or 5, wherein: and (3) by taking the mass of the mixed material as 100%, the copper slag accounts for 35% -40%, the fluxing agent accounts for 5-10%, and the balance is pyrolytic solid residues.
7. The method for recovering valuable metals from copper-containing electronic scrap as claimed in claim 1, wherein: the temperature of the oxygen-enriched top-blown smelting in the step (4) is 1250-1400 ℃, and the oxygen-enriched concentration is 40-70%.
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| CN202011490908.7A CN112708766A (en) | 2020-12-17 | 2020-12-17 | Method for recovering valuable metals in copper-containing electronic waste |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113617788A (en) * | 2021-06-29 | 2021-11-09 | 北京大学 | Method for comprehensively recovering electronic waste by using plasma technology |
| CN114480848A (en) * | 2021-12-30 | 2022-05-13 | 荆门格林循环电子废弃物处置有限公司 | Smelting treatment method for waste circuit board |
| CN114990349A (en) * | 2022-08-04 | 2022-09-02 | 中南大学 | Method for regenerating copper by pyrolyzing organic coating copper-based waste material |
| CN115029553A (en) * | 2022-01-07 | 2022-09-09 | 昆明理工大学 | Method for cooperatively treating copper-containing electronic waste through oxygen-enriched bottom blowing smelting |
| WO2023087114A1 (en) * | 2021-11-22 | 2023-05-25 | Pyrocycle Inc. | A process for recovering a metallic fraction from electronic waste and producing value-added products |
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| CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
| CN113617788A (en) * | 2021-06-29 | 2021-11-09 | 北京大学 | Method for comprehensively recovering electronic waste by using plasma technology |
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| CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
| CN113617788A (en) * | 2021-06-29 | 2021-11-09 | 北京大学 | Method for comprehensively recovering electronic waste by using plasma technology |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113617788A (en) * | 2021-06-29 | 2021-11-09 | 北京大学 | Method for comprehensively recovering electronic waste by using plasma technology |
| WO2023087114A1 (en) * | 2021-11-22 | 2023-05-25 | Pyrocycle Inc. | A process for recovering a metallic fraction from electronic waste and producing value-added products |
| CN114480848A (en) * | 2021-12-30 | 2022-05-13 | 荆门格林循环电子废弃物处置有限公司 | Smelting treatment method for waste circuit board |
| CN115029553A (en) * | 2022-01-07 | 2022-09-09 | 昆明理工大学 | Method for cooperatively treating copper-containing electronic waste through oxygen-enriched bottom blowing smelting |
| CN114990349A (en) * | 2022-08-04 | 2022-09-02 | 中南大学 | Method for regenerating copper by pyrolyzing organic coating copper-based waste material |
| CN114990349B (en) * | 2022-08-04 | 2022-11-04 | 中南大学 | Method for regenerating copper by pyrolyzing copper-based waste material of organic coating |
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Application publication date: 20210427 |