CN110863107B - Method for recovering silver from silver-containing electric contact composite material by using silver-tungsten framework - Google Patents
Method for recovering silver from silver-containing electric contact composite material by using silver-tungsten framework Download PDFInfo
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- CN110863107B CN110863107B CN201911017537.8A CN201911017537A CN110863107B CN 110863107 B CN110863107 B CN 110863107B CN 201911017537 A CN201911017537 A CN 201911017537A CN 110863107 B CN110863107 B CN 110863107B
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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
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
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Abstract
The invention discloses a method for recovering silver from a silver-containing electric contact composite material by utilizing a silver-tungsten framework, wherein the silver-containing electric contact composite material is formed by compounding a silver layer and at least one non-silver metal layer in a non-alloy state laminating or embedding manner, and the method comprises the following steps: contacting one side of a silver layer or a silver-based alloy layer of the silver-containing electric contact composite material with a silver-tungsten framework, placing the silver-containing electric contact composite material and the silver-tungsten framework in a high-temperature hydrogen furnace integrally, and setting the temperature to be higher than the melting point temperature of silver and lower than the melting point temperature of non-silver alloy components and non-silver metals of the silver-based alloy; melting silver in the silver layer or the silver-based alloy layer, infiltrating the silver into the silver-tungsten framework, cooling and discharging; then the silver-tungsten skeleton infiltrated with silver is placed in an electrolytic bath, and electrolytic silver powder is separated out from the cathode. The method has the advantages that the method does not need traditional chemical reagents such as nitric acid, concentrated sulfuric acid and the like, is beneficial to environmental protection treatment, and has low recovery cost and great industrial value.
Description
Technical Field
The invention belongs to the field of precious metal recovery, and particularly relates to a method for recovering silver from a silver-containing electric contact composite material by using a silver-tungsten framework.
Background
The silver and silver-based alloy composite copper, composite iron or composite nickel and other electrical contact materials are widely applied to relays, contactors, miniature switches, temperature controllers and the like, and meet the conductivity of products. However, in the production process, leftover materials and waste products are inevitable, and silver belongs to noble metals and needs to be recycled.
At present, the methods for recovering silver from silver-containing electric contact composite materials mainly comprise a nitric acid total dissolution method and a selective dissolution method. Because the silver content in the silver scraps is low, if a total nitric acid dissolving method is adopted, a large amount of nitric acid is consumed, the environment-friendly treatment capacity is large, while the selective dissolving method generally selects to dissolve silver, so that the consumption of nitric acid is low, and other composite metals can also be recovered, but chemical reagents used as passivators are used in a large amount, such as concentrated sulfuric acid and nitric acid mixed acid, so that the separation and recovery of copper and iron of silver and silver-based alloy composite copper materials and silver-based alloy composite iron materials can be realized, but the use amount of the concentrated sulfuric acid used as a passivator is large.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide the method for recovering silver from the silver-containing electric contact composite material by using the silver-tungsten framework, the method does not need traditional chemical reagents such as nitric acid, concentrated sulfuric acid and the like, is beneficial to environment-friendly treatment, and has low recovery cost and high industrial value.
In order to achieve the purpose of the invention, the technical scheme of the invention is a method for recovering silver from a silver-containing electric contact composite material by using a silver-tungsten framework, wherein the silver-containing electric contact composite material is formed by laminating a silver layer and at least one non-silver metal layer in a non-alloy state or compositing the silver-based alloy layer and at least one non-silver metal layer in a non-alloy state or compositing the non-silver metal layer in a mosaic manner, and the melting point of the non-silver metal is greater than that of the silver;
the method comprises the following steps:
(1) contacting one side of a silver layer or a silver-based alloy layer of the silver-containing electric contact composite material with a silver-tungsten framework, placing the silver-containing electric contact composite material and the silver-tungsten framework in a high-temperature hydrogen furnace integrally, and setting the temperature to be higher than the melting point temperature of silver and lower than the melting point temperature of non-silver alloy components and non-silver metals of the silver-based alloy; melting silver in the silver layer or the silver-based alloy layer, infiltrating the silver into the silver-tungsten framework, cooling and discharging;
(2) separating and recovering silver-tungsten skeleton infiltrated with silver and other unmelted components in the silver-containing electric contact composite material;
(3) and placing the silver-tungsten skeleton infiltrated with silver in an electrolytic bath, taking silver nitrate as mother liquor and the silver-tungsten skeleton as an anode, electrochemically dissolving the infiltrated silver in the silver-tungsten skeleton into electrolyte, and separating out electrolytic silver powder from the cathode.
(4) After electrolysis is carried out for a period of time, the electrolysis is stopped, the silver-tungsten framework is taken out and recycled in the step (1), and the silver ingot is smelted by the electrolytic silver powder;
further setting that the silver-tungsten framework in the step (1) contains 5-50% of silver;
the silver-tungsten framework in the step (1) is prepared by mixing, pressing and sintering, and the shape, length, width and thickness of the silver-tungsten framework are determined according to the size of the electrolytic cell, so that the optimal current density in the electrolytic process is ensured;
the method of the invention is that one side of the silver layer or the silver-based alloy layer of the silver-containing electric contact composite material is contacted with the silver-tungsten framework, and the furnace temperature is set above the melting point of silver and below the melting point of other composite metals in a high-temperature hydrogen furnace. Under the capillary action of the silver-tungsten framework, the silver layer in the composite material is melted into silver liquid which is gradually absorbed into the silver-tungsten framework, so that the separation of silver and other metals is realized. Then putting the silver-tungsten framework absorbed with the silver layer into an electrolytic tank, taking silver nitrate as mother liquor, taking the silver-tungsten framework as an anode, electrochemically dissolving silver in the silver-tungsten framework into electrolyte, reducing the cathode to separate out electrolytic silver powder, wherein tungsten cannot be dissolved into an ionic state in an acidic medium, has low acidity and can generate WO2、W2O5、WO3And the like, and can serve as an oxide film covering the surface of tungsten to inhibit electrochemical dissolution of tungsten. After a period of electrolysis, the silver content in the silver-tungsten framework is reduced, the produced electrolytic silver powder is cast into silver ingots, and the silver-tungsten framework after being taken out of the electrolytic bath is continuously recycled for recovering silver in the composite material.
Compared with the prior art, the invention has the advantages and positive effects that: 1. silver and silver-based alloy and other metals form a silver layer in the composite material, and the silver and other metals in the composite material can be separated and recovered without using a chemical reagent such as nitric acid, so that the environment-friendly treatment is facilitated, and the environment is protected; 2. the production process is reduced, the production period is shortened, and the recovery cost is reduced. If the silver is recovered by adopting a chemical reagent wet method, the obtained silver powder needs to be smelted into an electrolytic plate, and the electrolytic silver powder with high purity and few impurities can be obtained through an electrolysis process, so that the process is complex and the production period is long.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a process scheme of example 1;
FIG. 2 is a process scheme for example 2;
FIG. 3 is a process scheme for example 3;
figure 4 is a process scheme for example 4.
Detailed Description
The technical solutions of the present invention are further described below with reference to examples, which are only used for explaining the present invention and are not used for limiting the scope of the present invention.
The silver-tungsten skeleton used in the above embodiment of the present invention has a capillary structure, because silver-tungsten products in the industry are generally prepared by mixing powder, pressing and sintering, and have both a capillary structure and capillary force.
Example one
(1) A layer of silver-nickel composite iron material with silver content of 10% is laid on the silver-tungsten framework, and then the silver-tungsten framework is covered. Putting the composite material into a continuous pushing type hydrogen furnace for infiltration, setting the temperature of an effective temperature zone to be 1050 ℃, and setting the time of the composite material in the effective temperature zone to be 0.5 h;
(2) after the materials are taken out of the furnace, collecting and recovering iron scraps, putting a silver-tungsten framework into an electrolytic bath for electrolysis, taking silver nitrate as an electrolysis mother solution, putting the silver-tungsten framework into a titanium basket as an anode, and taking a titanium plate as a cathode;
(3) the current density was set at 200A/m2Stopping electrolysis after 24 hours, cleaning the electrolytic silver powder, then performing melt casting to obtain silver ingots, taking the silver-tungsten framework out of the electrolytic bath, cleaning the electrolytic bath with pure water, and then circulating the step (1);
the process route is shown in figure 1.
Example two
(1) A layer of silver composite copper material with 15% silver content is paved on the silver-tungsten framework, and then the silver-tungsten framework is covered. Putting the composite material into a continuous pushing type hydrogen furnace for infiltration, setting the temperature of an effective temperature zone to be 1000 ℃, and setting the time of the composite material in the effective temperature zone to be 0.5 h;
(2) after the copper scraps are taken out of the furnace, collecting and recovering the copper scraps, putting a silver-tungsten framework into an electrolytic bath for electrolysis, taking silver nitrate as an electrolysis mother solution, putting the silver-tungsten framework into a titanium basket as an anode, and taking a titanium plate as a cathode;
(3) the current density was set at 200A/m2Stopping electrolysis after 24 hours, cleaning the electrolytic silver powder, then performing melt casting to obtain silver ingots, taking the silver-tungsten framework out of the electrolytic bath, cleaning the electrolytic bath with pure water, and then circulating the step (1);
the process route is shown in figure 2.
EXAMPLE III
(1) A layer of silver-copper-iron three-composite material with silver content of 10% is paved on the silver-tungsten framework, and then the silver-tungsten framework is covered. Putting the composite material into a continuous pushing type hydrogen furnace for infiltration, setting the temperature of an effective temperature zone to be 1000 ℃, and setting the time of the composite material in the effective temperature zone to be 0.5 h;
(2) after the copper and iron scraps are taken out of the furnace, the copper and iron scraps are collected and recovered, a silver-tungsten framework is placed in an electrolytic bath for electrolysis, silver nitrate is used as an electrolysis mother solution, the silver-tungsten framework is placed in a titanium basket as an anode, and a titanium plate is used as a cathode;
(3) the current density was set at 200A/m2Stopping electrolysis after 24 hours, cleaning the electrolytic silver powder, then performing melt casting to obtain silver ingots, taking the silver-tungsten framework out of the electrolytic bath, cleaning the electrolytic bath with pure water, and then circulating the step (1);
the process route is shown in figure 3.
Example four
(1) A layer of silver-copper-silver three-composite material with silver content of 20% is paved on the silver-tungsten framework, and then the silver-tungsten framework is covered. Putting the composite material into a continuous pushing type hydrogen furnace for infiltration, setting the temperature of an effective temperature zone to be 1000 ℃, and setting the time of the composite material in the effective temperature zone to be 0.5 h;
(2) after the copper scraps are taken out of the furnace, collecting and recovering the copper scraps, putting a silver-tungsten framework into an electrolytic bath for electrolysis, taking silver nitrate as an electrolysis mother solution, putting the silver-tungsten framework into a titanium basket as an anode, and taking a titanium plate as a cathode;
(3) the current density was set at 200A/m2Stopping electrolysis after 24 hours, cleaning the electrolytic silver powder, then performing melt casting to obtain silver ingots, taking the silver-tungsten framework out of the electrolytic bath, cleaning the electrolytic bath with pure water, and then circulating the step (1);
the process route is shown in figure 4.
Claims (2)
1. A method for recovering silver from a silver-containing electric contact composite material by using a silver-tungsten framework is characterized by comprising the following steps of: the silver-containing electric contact composite material is formed by compounding a silver layer and at least one non-silver metal layer in a non-alloy state laminating or embedding manner, or compounding a silver-based alloy layer and at least one non-silver metal layer in a non-alloy state laminating or embedding manner, and the melting point of the non-silver metal is greater than that of silver;
the method comprises the following steps:
(1) contacting one side of a silver layer or a silver-based alloy layer of the silver-containing electric contact composite material with a silver-tungsten framework, placing the silver-containing electric contact composite material and the silver-tungsten framework in a high-temperature hydrogen furnace integrally, and setting the temperature to be higher than the melting point temperature of silver and lower than the melting point temperature of non-silver alloy components and non-silver metals of the silver-based alloy; melting silver in the silver layer or the silver-based alloy layer, infiltrating the silver into the silver-tungsten framework, cooling and discharging;
(2) separating and recovering silver-tungsten skeleton infiltrated with silver and other unmelted components in the silver-containing electric contact composite material;
(3) placing the silver-tungsten framework infiltrated with silver in an electrolytic bath, taking silver nitrate as mother liquor and the silver-tungsten framework as an anode, electrochemically dissolving the infiltrated silver in the silver-tungsten framework into electrolyte, and separating electrolytic silver powder from the cathode;
the silver content of the silver-tungsten skeleton in the step (1) is 5-50 percent;
the silver-tungsten framework in the step (1) is prepared by mixing, pressing and sintering, and the shape, length, width and thickness of the silver-tungsten framework are determined according to the size of the electrolytic cell, so that the optimal current density in the electrolytic process is ensured.
2. The method for recovering silver from the silver-containing electric contact composite material by using the silver-tungsten framework as claimed in claim 1, further comprising the step of stopping electrolysis after the electrolysis in the step (4) is completed, taking out the silver-tungsten framework for recycling in the step (1), and smelting silver ingots by using the electrolytic silver powder.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451185A (en) * | 2014-12-19 | 2015-03-25 | 桂林电器科学研究院有限公司 | Method for recovering silver by smelting silver-nickel scrap material |
| CN106191920A (en) * | 2016-08-13 | 2016-12-07 | 福达合金材料股份有限公司 | A kind of method of silver tungsten waste recovery recycling |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451185A (en) * | 2014-12-19 | 2015-03-25 | 桂林电器科学研究院有限公司 | Method for recovering silver by smelting silver-nickel scrap material |
| CN106191920A (en) * | 2016-08-13 | 2016-12-07 | 福达合金材料股份有限公司 | A kind of method of silver tungsten waste recovery recycling |
Non-Patent Citations (1)
| Title |
|---|
| "报废银钨触头回收银和钨的工艺研究";王琪 等;《稀有金属材料与工程》;20111031;第40卷(第10期);正文第1817-1821页 * |
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Effective date of registration: 20220916 Address after: 325025 No. 308, Binhai fifth road, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province Patentee after: Zhejiang Fuda alloy material technology Co.,Ltd. Address before: No. 518, Binhai 4th Road, Binhai Park, Wenzhou Economic and Technological Development Zone, Zhejiang Province, 325000 Patentee before: FUDA ALLOY MATERIALS Co.,Ltd. |
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