CN112030002A - Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards - Google Patents
Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards Download PDFInfo
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- CN112030002A CN112030002A CN202010947863.5A CN202010947863A CN112030002A CN 112030002 A CN112030002 A CN 112030002A CN 202010947863 A CN202010947863 A CN 202010947863A CN 112030002 A CN112030002 A CN 112030002A
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- smelting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
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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
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- 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
Abstract
The invention discloses a method for producing blister copper from waste circuit boards by direct oxygen-enriched smelting, which comprises the steps of adding crushed and dried waste circuit boards into a slagging molten pool, adding iron ore and calcium oxide to adjust the composition of a slag phase, introducing oxygen-enriched gas to carry out oxidation smelting, and separating after the oxidation smelting is finished to directly obtain blister copper and slag. According to the invention, the raw copper can be obtained from the waste circuit board through one-step high-temperature smelting, the operation process is simple, the pollution is small, the control is easy, the method is suitable for industrial application, the copper grade in the produced raw copper is greater than 96%, the metal yield can reach more than 90%, and the produced raw copper can directly enter a copper refining system to recover various valuable metals.
Description
Technical Field
The invention belongs to the field of solid waste resource recovery, and particularly relates to a method for producing blister copper from waste circuit boards by direct oxygen-enriched smelting.
Background
The electronic waste has complex and various components and mainly comprises ceramics, circuit boards, glass, plastics and the like. The printed circuit board is an important component in electronic and electrical equipment, is the most valuable part of electronic waste, and accounts for about 4-7% of the total amount of the electronic waste. In China, the amount of waste circuit boards to be processed reaches 500000 tons every year. The waste circuit board contains a large amount of recyclable resources, and is a huge secondary resource recycling treasure house. The waste circuit board contains about 28% of metal, 23% of plastic and 49% of ceramic material, and the recovery of valuable metal from the waste circuit board can bring huge economic benefit. Therefore, how to efficiently treat the waste circuit boards becomes a problem of close attention of many researchers at home and abroad.
The recovery processing method of the waste circuit board mainly comprises the methods of hydrometallurgy, microbial metallurgy, mechanical processing and the like, and the methods have respective advantages, disadvantages and limitations. The hydrometallurgy recovery technology mainly utilizes solvents such as cyanide, halide, thiourea and the like to leach valuable metals in the waste circuit boards, the recovery process is easy to control, but a large amount of waste water is generated, so that organic matters in the waste circuit boards cannot be fully utilized. The mechanical processing technology can only process a small range of waste circuit boards in a targeted manner, and has great limitation. Although the microbial technology has little pollution and little investment in the recovery process, the recovery period is long, and the large-scale factory application is difficult to realize.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a method for producing blister copper from waste circuit boards by direct oxygen-enriched smelting, wherein the method can realize one-step oxidation smelting to directly obtain blister copper, and simultaneously, impurity metal compounds in the waste circuit boards enter a slag phase and are well separated from a metal phase.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for producing blister copper from waste circuit boards by direct oxygen-enriched smelting comprises the steps of adding crushed and dried waste circuit boards into a slagging molten pool, adding iron ore and calcium oxide to adjust the composition of a slag phase, introducing oxygen-enriched gas to carry out oxidation smelting, and directly obtaining blister copper and furnace slag after the oxidation smelting is finished.
In the method, preferably, the slagging molten pool is added with slag fuming from the pyrometallurgical process to be used as bottom slag; the slag phase of the slag in the oxidation smelting process comprises the following components: fe and SiO2The mass ratio of CaO to SiO is 0.6-1.22The mass ratio is 0.25-0.85.
According to the characteristics of raw materials, the smelting process selects the fuming slag (Fe 27-30%, SiO) in the pyrometallurgical process217-20 percent of slag and 7-10 percent of CaO (fuming slag in the smelting process is mainly used as building materials or stockpiled and cannot be well utilized); the fuming slag has low content of valuable metal and relatively stable slag property, which is beneficial to the adjustment of slag phase composition in the subsequent smelting process), the slag phase composition is adjusted by adding iron ore and calcium oxide, and impurity metal compounds (such as SiO) in the waste circuit board in the smelting process2) Form FeO-CaO-SiO together with FeO, CaO and the like in the molten slag pool2The ternary slag is kept in a reasonable slag phase composition range, so that the slag in the smelting process has proper smelting temperature and smaller viscosity, and the slag has better fluidity and is beneficial to the smelting process. And valuable metals such as Cu, Sn, Ni, Bi, Au, Ag and the like in the waste circuit board have higher specific gravity than the molten slag, so that the separation of the metal produced in the smelting process and the slag is realized.
In the method, the temperature of oxidation smelting is preferably 1200-1300 ℃, and the smelting time is preferably 1-4 h. The smelting temperature is too high, which is beneficial to the smelting process, but the energy consumption is higher; the smelting temperature is too low, so that the slag is not completely melted in the smelting process, the viscosity is high, and the separation of the slag and the metal phase is not facilitated.
In the above method, preferably, the oxygen concentration in the oxygen-enriched gas is 20% to 50%.
In the method, preferably, the oxygen flow in the oxygen-enriched gas is 1L/min-3L/min. During the smelting process, too low or too high oxygen concentration can have certain influence on the copper grade in the metal phase and the metal yield. When the oxygen-material ratio is constant, when the oxygen concentration in the smelting process is too low, impurity metals in the raw materials cannot be oxidized and completely slagging is carried out, so that the grade of copper in the produced metal phase is influenced; the oxygen concentration is too high, so that valuable metals in the metal phase are oxidized and enter the slag phase to cause loss, and the metal yield is reduced.
In the method, preferably, the copper content in the waste circuit board accounts for 10-30% of the total amount of the waste circuit board.
The copper content in the crude copper obtained by the method is more than 96 percent.
Compared with the prior art, the invention has the advantages that:
according to the invention, the raw copper can be obtained from the waste circuit board through one-step high-temperature smelting, the operation process is simple, the pollution is small, the control is easy, the method is suitable for industrial application, the copper grade in the produced raw copper is greater than 96%, the metal yield can reach more than 90%, and the produced raw copper can directly enter a copper refining system to recover various valuable metals.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
A method for producing blister copper by direct oxygen-enriched smelting from waste circuit boards comprises the following steps:
the crushed and dried waste circuit board (the main components are Cu 25.80%, Al 5.70%, Si 18.80%, Sn 1.58%, Ca 10.34%, Ni 0.67%, B)i 0.03%, Br 9.24%, Pb 1.36%, Au 15g/t, Ag 160g/t) into a slagging molten pool (fuming slag needs to be added as bottom slag, which is beneficial to the control of the properties of the molten pool smelting slag and the separation of metal phase and slag phase), and the slag phase composition of the slag in the smelting process is as follows: fe and SiO2The mass ratio of CaO to SiO is 0.92Adding iron ore and calcium oxide according to the mass ratio of 0.65, smelting at 1200 ℃, introducing oxygen-enriched gas in the smelting process, controlling the oxygen concentration in the oxygen-enriched gas to be 50%, controlling the oxygen flow to be 1.2L/min, smelting at high temperature for 2.0h, and producing blister copper (main components of Cu96.50%, Sn0.88%, Pb 0.64%, Bi 0.40%, Ni 0.65%, Au 90g/t and Ag 460g/t) and slag (main components of Fe 30.25%, SiO 90g/t and Ag 460g/t)2 34.37％，CaO 19.75％，Al2O23.15 percent), the copper grade in the crude copper reaches 96.5 percent, and the metal yield is 82.5 percent.
Example 2:
a method for producing blister copper by direct oxygen-enriched smelting from waste circuit boards comprises the following steps:
adding the crushed and dried waste circuit board (the main components are Cu 25.80%, Al 5.70%, Si 18.80%, Sn 1.58%, Ca 10.34%, Ni 0.67%, Bi 0.03%, Br 9.24%, Pb 1.36%, Au 15g/t and Ag 160g/t) into a slagging molten pool (fuming slag is required to be added as bottom slag, which is beneficial to the control of the properties of the molten pool smelting slag and the separation of a metal phase and a slag phase), and according to the slag phase composition of the slag in the smelting process: fe and SiO2The mass ratio of CaO to SiO is 0.82Adding iron ore and calcium oxide according to the mass ratio of 0.45, smelting at the smelting temperature of 1250 ℃, introducing oxygen-enriched gas in the smelting process, controlling the oxygen concentration in the oxygen-enriched gas to be 50%, controlling the oxygen flow to be 1L/min, smelting for 3h, and producing blister copper (the main components of Cu 97.60%, Sn 0.40%, Pb 0.30%, Bi 0.50%, Ni 0.80%, Au 98g/t and Ag 440g/t) and furnace slag (the main components of Fe 32.30%, SiO 98g/t and Ag 440g/t)2 38.24％，CaO 17.35％，Al2O23.12 percent), the copper grade in the crude copper reaches 97.60 percent, and the metal yield is 91.50 percent.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (7)
1. A method for producing blister copper from waste circuit boards by direct oxygen-enriched smelting is characterized in that crushed and dried waste circuit boards are added into a slagging molten pool, iron ore and calcium oxide are added to adjust the composition of a slag phase, oxygen-enriched gas is introduced to carry out oxidation smelting, and separation is carried out after the oxidation smelting is finished to directly obtain blister copper and slag.
2. The method of claim 1, wherein the slag phase composition of the slag during the oxidizing smelting process is: fe and SiO2The mass ratio of CaO to SiO is 0.6-1.22The mass ratio is 0.25-0.85.
3. The method of claim 1, wherein the temperature of the oxidizing smelting is 1200 ℃ to 1300 ℃ and the smelting time is 1h to 4 h.
4. The method of any one of claims 1-3, wherein the oxygen-enriched gas has an oxygen concentration of 20% to 50%.
5. The method according to any one of claims 1 to 3, wherein the oxygen flow in the oxygen-enriched gas is between 1L/min and 3L/min.
6. The method according to any one of claims 1 to 3, wherein the waste circuit boards comprise the following main components: 10-30% of Cu, 3-7% of Al, 16-20% of Si, 1-3% of Sn, 8-12% of Ca, 0.5-1% of Ni, 0.01-0.05% of Bi, 7-10% of Br, 1-3% of Pb, 10-30g/t of Au and 200g/t of Ag 160-.
7. A method according to any one of claims 1-3, characterized in that the copper content in the blister copper obtained is above 96%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293303A (en) * | 2021-06-04 | 2021-08-24 | 江西理工大学 | Method for producing lead alloy by synergistically reducing and smelting waste lead paste |
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