CN112458288A - Method for recovering and preparing silver material from silver-containing waste material - Google Patents
Method for recovering and preparing silver material from silver-containing waste material Download PDFInfo
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- CN112458288A CN112458288A CN202011203306.9A CN202011203306A CN112458288A CN 112458288 A CN112458288 A CN 112458288A CN 202011203306 A CN202011203306 A CN 202011203306A CN 112458288 A CN112458288 A CN 112458288A
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for recovering and preparing silver materials from silver-containing waste materials, which comprises the following steps: s1, putting the silver-containing waste into a reactor, adding 30% nitric acid, heating for a first reaction to dissolve silver into silver ions, filtering, collecting filtrate, adding 30% nitric acid into filter residues, heating for a second reaction to dissolve again, and combining the filtrates; s2, adding sufficient sodium chloride into the filtrate obtained by combining the steps until the silver ions are completely precipitated, and filtering and cleaning the silver chloride precipitate; s3, uniformly mixing the silver chloride precipitate obtained in the step S2 with sodium carbonate and a reagent A, then placing the mixture into a high-temperature-resistant container, heating the mixture for thermal decomposition reaction, and directly casting the molten silver liquid to form a silver material, wherein the reagent A is one or a combination of more of fluorite, borax, sodium hydroxide and cryolite. The method has the advantages of simple process route, low treatment cost, greatly reduced wastewater discharge compared with the traditional reduction process, good silver separation effect and high silver recovery rate of more than 99 percent.
Description
Technical Field
The invention belongs to the field of precious metal metallurgy, and particularly relates to a method for recovering and preparing silver materials from silver-containing waste materials.
Background
Silver is a precious metal, because its excellent physical and chemical properties are widely used in the industries of materials, catalysts, energy sources and the like, the data shows that the silver consumption exceeds 1 ten thousand tons per year, and because the silver consumption is large, various leftover materials and scrapped products generated along with the silver consumption are not few, the regeneration work of the silver is particularly important, and the data shows that the annual regenerated silver yield exceeds 5000 tons in recent years. For waste materials with low silver content, pyrogenic processes are generally used for recovery, but pyrogenic recovery is limited in many areas due to environmental problems and the like. For scrap with silver content greater than 5%, wet recovery is generally recommended.
Most of the existing wet recovery processes are to leach silver by nitric acid, then precipitate sodium chloride, reduce the silver powder by a reducing agent, smelt the silver powder by an intermediate frequency furnace, and finally cast the silver liquid. The process flow is long, sodium hydroxide or ammonia water and organic reducing agents such as hydrazine hydrate, glucose, VC and the like are required to be added in the reduction process, the method is high in cost, and the reduced wastewater is high in salt content and COD content; more importantly, the water with high salt content is available, the biochemical system can not effectively remove COD in the water, and the cost for treating the COD in the wastewater is huge.
By search, chinese patent application publication No. CN109777959A discloses a method for recovering silver from a silver-containing waste catalyst in petrochemical industry, which is suitable for recovering silver from a silver-containing waste catalyst with alumina or silica as a carrier. The process route is as follows: waste silver catalyst → crushing → nitric acid leaching → sodium chloride silver sinking → iron plate replacement → melting ingot → metallic silver ingot product. According to the method, the conventional organic reducing agent is replaced by iron replacement, so that the generation of high-salt and high-COD wastewater is avoided, the use of hydrochloric acid is easy to corrode equipment, in addition, iron filings are easy to generate in the iron reduction process and are mixed into silver powder, and even if the silver powder is subsequently cleaned by dilute hydrochloric acid, the silver powder is not easy to clean, and the iron content in the silver powder is easy to exceed the standard.
Chinese patent application publication No. CN109402402A discloses a method for recovering gold and silver from gold, silver and copper alloy waste, in which the recovery of silver is directly performed by electrodeposition after silver is dissolved into silver nitrate, and this method lacks the process of sodium chloride precipitation for removing impurities, and for waste with complex components, even if the nitric acid leachate can be used for electrodeposition, the electrodeposition efficiency cannot be guaranteed, and in addition, for impurities with a potential close to silver, it cannot be removed, and the quality of silver products is affected, so this method can only recover specific waste.
Based on the reasons, the development of a new method with wide application range, low recovery cost and small environmental pollution is of great significance.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a method for recovering and preparing silver plates from silver-containing waste materials. The method directly shortens the procedures of smelting silver chloride into silver liquid and casting the silver liquid into a silver plate on the basis of the existing silver recovery process, and the procedures of smelting silver chloride into silver liquid and casting the silver liquid into the silver plate are directly shortened to the procedures of smelting silver chloride into silver liquid and casting the silver plate into the silver plate, so that the reduction procedure is omitted, the whole process does not generate high-salt and high-COD wastewater which is difficult to treat, the raw material cost is reduced, the wastewater treatment cost is reduced, the product quality is ensured, and the economic and social effects are improved.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
s1, putting the silver-containing waste into a reactor, adding 30% nitric acid, heating for a first reaction to dissolve silver into silver ions, filtering, collecting filtrate, adding 30% nitric acid into filter residues, heating for a second reaction to dissolve again, and combining the filtrates;
s2, adding sufficient sodium chloride into the filtrate obtained by combining the steps until the silver ions are completely precipitated, and filtering and cleaning the silver chloride precipitate;
s3, uniformly mixing the silver chloride precipitate obtained in the step S2 with sodium carbonate and a reagent A, then placing the mixture into a high-temperature-resistant container, heating the mixture for thermal decomposition reaction, and directly casting molten silver liquid to form silver ingots, wherein the reagent A is one or a combination of more of fluorite, borax, sodium hydroxide and cryolite.
Further setting the adding amount of 30% nitric acid for heating the primary reaction in the step S1 to be 1: 1-1.5 of the solid-to-liquid ratio by taking the silver-containing waste as molecules; in the step S1, the addition amount of the 30% nitric acid for the heating secondary reaction is 1/3-1/2 of the addition amount of the heating primary reaction.
The mass ratio of the added silver chloride, sodium carbonate and A reagent is further set as follows: 1:1 to 2:0.01 to 0.05.
The method has the beneficial effects that the method has wide application range and can be used for all the silver-containing wastes suitable for wet recovery. The method is characterized in that based on the existing silver recovery process, silver chloride is reduced into silver powder, the silver powder is smelted into silver liquid, the procedure of casting the silver liquid into a silver plate is directly shortened into the procedure of smelting the silver chloride into the silver liquid, and then casting the silver plate. The main principle of the method is that silver chloride reacts with sodium carbonate to generate silver carbonate, the silver carbonate is decomposed into silver oxide, and the silver oxide is continuously decomposed into silver at high temperature. The method saves the reduction process of the original process, does not generate high-salt and high-COD wastewater which is difficult to treat in the whole process, reduces the raw material cost and the wastewater treatment cost, ensures the product quality and improves the enterprise profit.
The method has the advantages of simple process route, low treatment cost, great reduction of wastewater discharge compared with the traditional reduction process, good silver separation effect, high silver recovery rate of more than 99 percent and high silver content of the product of more than 99.95 percent.
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 flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
(1) Putting 1kg of electrical contact waste containing silver and 80% into a stainless steel reactor, adding 1.5L of nitric acid with the concentration of 30%, heating for half an hour, filtering, collecting filtrate, adding 0.5L of nitric acid with the concentration of 30% into filter residue, soaking for half an hour, and mixing the filtrates. (2) And adding sufficient sodium chloride into the combined filtrate until the silver precipitate is complete, and filtering and cleaning the silver chloride precipitate. (3) Uniformly mixing the silver chloride precipitate, 2 times of sodium carbonate by mass and 0.01 times of reagent A by mass, putting the mixture into a graphite clay crucible, heating to 850 ℃, keeping the temperature for 1 hour, taking out the crucible, pouring the slag on the upper layer, and directly casting the molten silver liquid into a silver plate. The weight of the silver plate is 0.798kg, the recovery rate is 99.75 percent, and the silver content is 99.96 percent.
Example 2
(1) Putting 10kg of electrical contact waste containing 70% of silver into a stainless steel reactor, adding 15L of 30% nitric acid, heating for half an hour, filtering, collecting filtrate, adding 7L of 30% nitric acid into filter residue, soaking for half an hour, and mixing filtrates. (2) And adding sufficient sodium chloride into the combined filtrate until the silver precipitate is complete, and filtering and cleaning the silver chloride precipitate. (3) Uniformly mixing the silver chloride precipitate, 1.5 times of sodium carbonate by mass and 0.01 times of reagent A by mass, putting the mixture into a graphite clay crucible, heating to 850 ℃, keeping the temperature for 2 hours, taking out the crucible, pouring the slag on the upper layer, and directly casting the molten silver liquid into a silver plate. The weight of the silver plate is 6.96kg, the recovery rate is 99.42 percent, and the silver content is 99.95 percent.
Comparative example 1
(1) Putting 1kg of electrical contact waste containing silver and 80% into a stainless steel reactor, adding 15L of nitric acid with the concentration of 30%, heating for half an hour, filtering, collecting filtrate, adding 7L of nitric acid with the concentration of 30% into filter residue, soaking for half an hour, and mixing the filtrates. (2) And adding sufficient sodium chloride into the combined filtrate until the silver precipitate is complete, and filtering and cleaning the silver chloride precipitate. (3) Uniformly mixing the silver chloride precipitate, 0.5 times of sodium carbonate and 0.01 times of reagent A by mass, putting the mixture into a graphite clay crucible, heating to 850 ℃, keeping the temperature for 2 hours, taking out the crucible, pouring the slag on the upper layer, and directly casting the molten silver liquid into a silver plate. The weight of the silver plate is 0.48kg, the recovery rate is 60 percent, and the silver content is 99.95 percent.
Comparative example 2
(1) Putting 1kg of electrical contact waste containing silver and 80% into a stainless steel reactor, adding 15L of nitric acid with the concentration of 30%, heating for half an hour, filtering, collecting filtrate, adding 7L of nitric acid with the concentration of 30% into filter residue, soaking for half an hour, and mixing the filtrates. (2) And adding sufficient sodium chloride into the combined filtrate until the silver precipitate is complete, and filtering and cleaning the silver chloride precipitate. (3) Uniformly mixing the silver chloride precipitate with 2 times of sodium carbonate by mass, putting the mixture into a graphite clay crucible, heating to 850 ℃, keeping the temperature for 2 hours, taking out the crucible, pouring the slag on the upper layer, and directly casting the molten silver liquid into a silver plate. The weight of the silver plate is 0.62kg, the recovery rate is 77.5 percent, and the silver content is 99.98 percent.
Comparative example 3
(1) Putting 1kg of electrical contact waste containing silver and 80% into a stainless steel reactor, adding 15L of nitric acid with the concentration of 30%, heating for half an hour, filtering, collecting filtrate, adding 7L of nitric acid with the concentration of 30% into filter residue, soaking for half an hour, and mixing the filtrates. (2) And adding sufficient sodium chloride into the combined filtrate until the silver precipitate is complete, and filtering and cleaning the silver chloride precipitate. (3) Uniformly mixing the silver chloride precipitate with 2 times of sodium carbonate by mass, putting the mixture into a graphite clay crucible, heating to 1050 ℃, keeping the temperature for 2 hours, taking out the crucible, pouring the slag on the upper layer, and directly casting the molten silver liquid into a silver plate. The weight of the silver plate is 0.792kg, the recovery rate is 99 percent, and the silver content is 99.96 percent.
Through comparative analysis of the embodiment 1 and the comparative examples 1 to 3, the addition amount of sodium carbonate is very important, the addition amount of sodium carbonate is too small, the reaction is incomplete, the silver recovery rate is low, if the addition amount of sodium carbonate is too large, the slag amount is too large, and the silver yield in each furnace is too small, so that the production efficiency is influenced. Meanwhile, the addition of the reagent A is very important, and the reagent A can effectively reduce the reaction temperature, reduce the energy consumption and reduce the production cost.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (3)
1. A method for recovering and preparing silver materials from silver-containing waste materials is characterized by comprising the following steps:
s1, putting the silver-containing waste into a reactor, adding 30% nitric acid, heating for a first reaction to dissolve silver into silver ions, filtering, collecting filtrate, adding 30% nitric acid into filter residues, heating for a second reaction to dissolve again, and combining the filtrates;
s2, adding sufficient sodium chloride into the filtrate obtained by combining the steps until the silver ions are completely precipitated, and filtering and cleaning the silver chloride precipitate;
s3, uniformly mixing the silver chloride precipitate obtained in the step S2 with sodium carbonate and a reagent A, then placing the mixture into a high-temperature-resistant container, heating the mixture for thermal decomposition reaction, and directly casting molten silver liquid to form silver ingots, wherein the reagent A is one or a combination of more of fluorite, borax, sodium hydroxide and cryolite.
2. The method for recovering and preparing silver material from silver-containing waste material according to claim 1, wherein: in the step S1, the addition amount of 30% nitric acid for the primary heating reaction is 1: 1-1.5 of the solid-to-liquid ratio of the silver-containing waste serving as molecules; in the step S1, the addition amount of the 30% nitric acid for the heating secondary reaction is 1/3-1/2 of the addition amount of the heating primary reaction.
3. The method for recovering and preparing silver material from silver-containing waste material according to claim 1, wherein: the mass ratio of the added silver chloride to the added sodium carbonate to the added reagent A is as follows: 1:1 to 2:0.01 to 0.05.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011203306.9A CN112458288A (en) | 2020-11-02 | 2020-11-02 | Method for recovering and preparing silver material from silver-containing waste material |
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| CN202011203306.9A CN112458288A (en) | 2020-11-02 | 2020-11-02 | Method for recovering and preparing silver material from silver-containing waste material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981237A (en) * | 2021-10-09 | 2022-01-28 | 青海西钢特殊钢科技开发有限公司 | Method for recovering simple substance silver from overdue silver nitrate |
| CN114032389A (en) * | 2021-10-09 | 2022-02-11 | 青海西钢特殊钢科技开发有限公司 | Method for recovering simple substance silver from analysis waste liquid of manganese element in steel |
| CN114293023A (en) * | 2021-12-28 | 2022-04-08 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and palladium from silver and palladium-containing material |
| CN114477535A (en) * | 2022-01-22 | 2022-05-13 | 宿迁市兴立环保科技有限公司 | Cyclic dechlorination process for wastewater containing chlorine nitrate |
| CN114875246A (en) * | 2022-04-25 | 2022-08-09 | 江西耐华环保科技有限公司 | Pretreatment recovery method of waste silver-aluminum catalyst |
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| CN102373338A (en) * | 2010-08-20 | 2012-03-14 | 沈阳有色金属研究院 | Method for extracting metallic silver from silver chloride sediment |
| CN109536726A (en) * | 2019-01-14 | 2019-03-29 | 北京科技大学 | A kind of recovery method of argentiferous dead catalyst |
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2020
- 2020-11-02 CN CN202011203306.9A patent/CN112458288A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102373338A (en) * | 2010-08-20 | 2012-03-14 | 沈阳有色金属研究院 | Method for extracting metallic silver from silver chloride sediment |
| CN109536726A (en) * | 2019-01-14 | 2019-03-29 | 北京科技大学 | A kind of recovery method of argentiferous dead catalyst |
Non-Patent Citations (1)
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| 马荣骏: "《循环经济的二次资源金属回收》", 30 June 2014 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981237A (en) * | 2021-10-09 | 2022-01-28 | 青海西钢特殊钢科技开发有限公司 | Method for recovering simple substance silver from overdue silver nitrate |
| CN114032389A (en) * | 2021-10-09 | 2022-02-11 | 青海西钢特殊钢科技开发有限公司 | Method for recovering simple substance silver from analysis waste liquid of manganese element in steel |
| CN114293023A (en) * | 2021-12-28 | 2022-04-08 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and palladium from silver and palladium-containing material |
| CN114477535A (en) * | 2022-01-22 | 2022-05-13 | 宿迁市兴立环保科技有限公司 | Cyclic dechlorination process for wastewater containing chlorine nitrate |
| CN114477535B (en) * | 2022-01-22 | 2023-12-12 | 宿迁市兴立环保科技有限公司 | Chlorine-containing nitrate wastewater circulating chlorine removal process |
| CN114875246A (en) * | 2022-04-25 | 2022-08-09 | 江西耐华环保科技有限公司 | Pretreatment recovery method of waste silver-aluminum catalyst |
| CN114875246B (en) * | 2022-04-25 | 2024-05-14 | 江西耐华环保科技有限公司 | Pretreatment recovery method of waste silver-aluminum catalyst |
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Application publication date: 20210309 |