CN104894383A - Leaching method of gold and copper in gold-contained electronic waste - Google Patents
Leaching method of gold and copper in gold-contained electronic waste Download PDFInfo
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- CN104894383A CN104894383A CN201510311770.2A CN201510311770A CN104894383A CN 104894383 A CN104894383 A CN 104894383A CN 201510311770 A CN201510311770 A CN 201510311770A CN 104894383 A CN104894383 A CN 104894383A
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Abstract
The invention discloses a leaching method of gold and copper in a gold-contained electronic waste. The gold-contained electronic waste is crushed, and the particle size of crushed particles is not more than 2 mm; then, the ball-milling treatment is performed, and the particle size is not more than 1 mm after the ball-milling treatment; powder obtained by the ball-milling treatment is added in sulfuric acid solution with a concentration of 130-170 g/L for copper leaching to obtain copper-enriched solution and copper leaching slag; and finally, the chlorination gold leaching is performed for the copper leaching slag to obtain gold-enriched solution. The method realizes the separation of copper and gold; the obtained copper-enriched solution and gold-enriched solution can be deeply treated to obtain gold and copper simple substances; and in the separation process, such other metals as lead and tin can be separated through controlling the redox potential.
Description
Technical field
The present invention relates to a kind of leaching method containing gold and copper in golden electron wastes, is the method to being separated leaching with the high-level efficiency of copper containing gold in golden electron wastes.Belong to the industrial waste process in environmental protection technical field, resource utilization field.
Background technology
The title that electron wastes has " mine, city ", mainly comprises the old computer, the communication equipment such as mobile phone, televisor, refrigerator, air-conditioning, the household electrical appliance such as washing machine and other the electronic machine etc. that go out of use in productive life.Containing multiple metals with high recovery value such as gold, copper, aluminium in electron wastes, the taste of its metal is tens even hundred times of native deposits, therefore, the metal in recycling electron wastes has great importance for the harmless treatment of electronic waste.The total amount of waste and old circuit board accounts for 4% of all electron wastes.Metal usually containing 40% in circuit card, what in various metal, content was the highest is copper, and recovery value the highest be gold.
Consider from environmental, containing multiple harmful substances in waste and old circuit board, wherein comprise the organic constituent that the heavy metal elements such as lead, chromium, cadmium, mercury and brominated flame retardant, polycyclic aromatic hydrocarbons, polychlorobiphenyl etc. are poisonous.Most poisonous and harmful component all has biological accumulation, is difficult to be degraded by physical environment simultaneously.If dealt with improperly, once entered environment, by the extremely serious ecotope of generation and human health risk.
Consider from the angle of resource, the content of the Jin Hetong in waste and old circuit board is respectively up to 3300g/t and 26.8%, and the content of the especially precious metal such as Au, Ag, Pd of metallic element is wherein all higher than the taste in other corresponding ores.Meanwhile, relative to general ore, other components of waste and old circuit board are very little on the impact of metal leaching process, and do not need complicated preprocessing process, if reasonably recycle it, its economic benefit is very considerable.
But for gold and the leaching of copper in waste and old circuit board, what be most widely used at present be Wet-process metallurgy method is cyanide process and chloroazotic acid method.Although cyanide process technical process is simple, leaching rate is high, and cyanide process can produce containing hypertoxic cyanide wastewater, causes secondary pollution; Chloroazotic acid method has good solute effect to Jin Hetong, but the corrodibility of chloroazotic acid is strong, requires very high, can produce a large amount of strongly acid wastewater simultaneously to the erosion resistance of equipment.It is fast that By Thiourea-uv Method has leaching efficiency, the advantages such as leach liquor is nontoxic, but thiocarbamide is expensive, and consumption is large, and thiocarbamide easily resolves into dme, adds production cost; Thiosulphate consumption is large, and process costs is high.
Chinese patent " a kind of method reclaiming various metals from electron wastes " (patent No. 2013105499577) by electron wastes after crushed, dissolve various metals composition by nitric acid liquid leaching and enter solution, utilize Polyviologen functional high molecule material process gained solution, the non-ferrous metal enrichments such as copper-lead nickel are also separated; Residue after the leaching of hydrochloric acid chloroazotic acid, filters direct separating plastic component respectively; Utilize the solution of the matrix material process gained containing heteroatomic conducting function electronic material or this conducting function polymer and Graphene, enrichment the precious metal ion that reduces, then after high melt, obtain highly purified noble metal.In this method, adopt hydrochloric acid and chloroazotic acid leach residue, strong acid waste water can be produced in leaching process, cause secondary pollution; Adopt high melt to obtain highly purified noble metal, in high melt process, inevitably produce obnoxious flavour, and the method energy consumption is large, is not suitable for all electron wastes.
It is get gold leaching solution after naked state that electron wastes is processed into gold by Chinese patent " a kind of for leaching gold leaching solution golden in electronic waste and method " (patent No. 2014101662305), by solid-liquid mass ratio 1:(5-10), at 25 ~ 70 DEG C of temperature, heated and stirred 0.5 ~ 2h, gold leaching rate reaches more than 99%, and gold leaching solution is the ammonium chloride of 1% ~ 10% in this method, the sulfuric acid of 5% ~ 25%, the hydrogen peroxide of 0.1% ~ 2%, the nitric acid of 5% ~ 25%.In this method, adopt gold leaching solution to soak golden process and copper is not leached, the subsequent recovery of gold is brought inconvenience.
Chinese patent " a kind of novel microemulsion liquid is to Au plasma method in electron wastes " (patent No. 2014100589266) adds after then chloroazotic acid process evaporates chloroazotic acid count hydrochloric acid aftertreatment by pulverizing the electron wastes after drying, add deionized water after evaporating hydrochloric acid soln to filter, filtrate is Au (III) ion filtrate; Be the hexanaphthene of volume ratio 7:3 by [C14mim] Br additional proportion, dissolve in the mixed phase of n-hexyl alcohol, then add HCl process, be separated organic phase and form microemulsion with being separated after hydrochloric acid aqueous phase, shake extracting gold ion by after gold ion working fluid and micro emulsion liquid-phase mixing.Adopt in this method organism relatively gold extract, poisonous and hazardous material can be produced in leaching process, and extraction liquid not easily processes, can secondary pollution be caused; Electron wastes after adopting chloroazotic acid process to pulverize, produces volatile gases material in process and evaporative process, causes environmental pollution; And copper is not leached in Au plasma process, the leaching rate of impact gold.
So no matter the gold in recovery waste and old circuit board and copper consider all have very large realistic meaning, also meet the theory of recycling economy from environmental or resource view.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of chlorination process leaching technology containing gold and copper in golden electronic waste, the high efficiency separation leaching realized containing gold and copper in golden electron wastes is extracted by mechanical approach pre-treatment-chlorination process, and to leached mud recycling, thus realize containing the resource utilization of gold in golden electron wastes and copper extraction and innoxious.
Technical solution of the present invention is as follows:
Containing a leaching method for gold and copper in golden electron wastes, it is characterized in that, comprise the steps:
1. will put into shredder assembly containing golden electron wastes and carry out closed break process, produce crushed particles, the particle diameter≤2mm of crushed particles;
2. crushed particles be conveyed in ball mill and carry out ball-milling processing, the particle diameter of crushed particles is reduced further, and after ball-milling processing, particle diameter≤1mm, obtains ball-milled powder;
3. ball-milled powder is joined in 130 ~ 170g/L sulphuric acid soln, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 60 ~ 100 DEG C, reaction times is 6 ~ 10h, and make solution system current potential maintain between 400 ~ 600mV by the add-on controlling sodium chlorate, obtain rich copper solutions and leaching copper ashes;
4. the process of chlorination leaching gold is carried out after leaching copper ashes being dried, leaching liquid is the sulphuric acid soln of 80 ~ 120g/L, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 30 ~ 60 DEG C, reaction times is 70 ~ 100min, and make solution system current potential maintain between 800-1200mV by the add-on controlling sodium chlorate, obtain rich gold solution.
Preferably, the particle diameter of described crushed particles is 1.49mm, and after ball-milling processing, particle diameter is 0.64mm.
Preferably, described step 3. in leaching liquid be the sulphuric acid soln of 150g/L, solid-to-liquid ratio is 1:8, and temperature of reaction is 80 DEG C, and the reaction times is 8h.
Preferably, described step 4. in leaching liquid be the sulphuric acid soln of 100g/L, solid-to-liquid ratio is 1:8, and temperature of reaction is 40 DEG C, and the reaction times is 90min.
The concrete treating processes of the present invention and reclaim principle as follows:
1, shredder assembly will be put into containing golden electronic waste thing and carry out closed break process, and make the particle diameter of crushed particles meet ball-milling processing requirement; Particle diameter≤the 2mm of crushed particles;
2, the particle transport after fragmentation is entered in ball mill to carry out ball-milling processing, reduce the particle after fragmentation further, to improve the chlorination extraction rate of copper and gold; Particle diameter≤1mm after ball-milling processing;
3, control current potential is carried out to the powder after ball milling and divide copper, digestion agent is the sulphuric acid soln of 130 ~ 170g/L, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 60 ~ 100 DEG C, reaction times is 6 ~ 10h, and by the add-on controlling sodium chlorate, solution system current potential is maintained between 400 ~ 600mV, thus obtain rich copper solutions and leaching copper ashes; Leaching copper ashes repeatedly can repeat leaching, and copper leaching liquid becomes monomer through condensing crystal.
4, gold process is soaked after leaching copper ashes being dried, leaching liquid is the sulphuric acid soln of 80 ~ 120g/L, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 30 ~ 60 DEG C, reaction times is 70 ~ 100min, and make solution system current potential maintain between 800-1200mV by the add-on controlling sodium chlorate, obtain rich gold solution and the golden slag of leaching; Rich gold solution carries out the recovery of gold through the method such as ion-exchange, extraction, soak golden slag and repeatedly can repeat leaching.
Compared with prior art, the invention has the beneficial effects as follows that the high and treating processes of the leaching rate of Jin Hetong cleans, in environment, do not discharge any hazardous and noxious substances to there is efficient, environmental protection, feature that resource utilization degree is high, be applicable to heavy industrialization application.
Accompanying drawing explanation
Fig. 1 is the schema that the present invention contains the leaching method of gold and copper in golden electron wastes.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but should not limit the scope of the invention with this.
Refer to Fig. 1, Fig. 1 is the chlorination process leaching technology that the present invention contains gold and copper in golden electron wastes, as shown in the figure, a kind of chlorination leaching method containing gold and copper in golden electron wastes, comprise fragmentation-ball milling-leaching copper-soak golden process, shearing-crushing device will be put into containing golden electron wastes and carry out closed break process, and make crushed particles meet ball-milling processing requirement, the particle diameter≤2mm of crushed particles; Then the crushed particles of broken gained is carried out ball-milling processing, to reduce the particle diameter of circuit card particle further, thus be more conducive to the lixiviate of copper and gold, particle diameter≤1mm after ball-milling processing; Afterwards the ball-milled powder of ball-milling processing gained being joined concentration is carry out leaching copper in the sulphuric acid soln of 130 ~ 170g/L, solid-to-liquid ratio 1:(6 ~ 10), and by the add-on controlling sodium chlorate, the redox potential of reaction soln is remained on 400 ~ 600mv, reaction times is 6 ~ 10h, temperature of reaction is 60 ~ 100 DEG C, obtains rich copper solutions and leaching copper ashes; Finally chlorination leaching gold is carried out to the leaching copper ashes after oven dry, leaching liquid is the sulphuric acid soln of 80 ~ 120g/L, solid-to-liquid ratio 1:(6 ~ 10), and maintain the redox potential of reaction soln at 800-1200mv by the add-on controlling sodium chlorate, reaction times is 70 ~ 100min, temperature of reaction is 30 ~ 60 DEG C, obtains rich gold solution.
Embodiment 1
To put into shearing-crushing device containing golden waste and old circuit board and carry out closed break process, the particle diameter of crushed particles is 1.49mm, collects the circuit card particle after fragmentation; Then the circuit card particle transport after fragmentation entered in the hybrid ball mill of RetschMM400 to carry out ball-milling processing, after ball-milling processing, particle diameter is 0.64mm; Afterwards the circuit card powder of ball-milling processing gained is carried out control current potential leaching copper, the sulphuric acid soln that concentration is 150g/L is added with the solid-to-liquid ratio of 1:8, temperature of reaction controls be 80 DEG C and keep constant temperature, solution system current potential is made to maintain between 400-600mV by the add-on controlling sodium chlorate, leaching time is 8h, obtain rich copper solutions and leaching copper ashes after filtration respectively, the leaching yield of copper is 83.25%; The process of control current potential leaching gold is carried out after finally point copper ashes being dried, add the sulphuric acid soln 40ml of 100g/L, it is 40 DEG C of constant temperature that temperature of reaction controls, leaching time is 90min, and make solution system current potential maintain between 800 ~ 1200mV by the add-on controlling sodium chlorate, obtain rich gold solution after filtration, the leaching yield of gold is 99%.
Should be understood that, to those skilled in the art, can be improved according to the above description or change, and all these improve and change the protection domain that all should belong to claims of the present invention.
Claims (4)
1., containing a leaching method for gold and copper in golden electron wastes, it is characterized in that, comprise the steps:
1. will put into shredder assembly containing golden electron wastes and carry out closed break process, produce crushed particles, the particle diameter≤2mm of crushed particles;
2. the particle transport of fragmentation entered in ball mill device to carry out ball-milling processing, the particle diameter of crushed particles is reduced further, and after ball-milling processing, particle diameter≤1mm, obtains ball-milled powder;
3. ball-milled powder is joined in 130 ~ 170g/L copper-bath, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 60 ~ 100 DEG C, reaction times is 6 ~ 10h, and make solution system current potential maintain between 400 ~ 600mV by the add-on controlling sodium chlorate, obtain rich copper solutions and leaching copper ashes;
4. the process of chlorination leaching gold is carried out after leaching copper ashes being dried, leaching liquid is the sulphuric acid soln of 80 ~ 120g/L, solid-to-liquid ratio 1:(6 ~ 10), temperature of reaction is 30 ~ 60 DEG C, reaction times is 70 ~ 100min, and make solution system current potential maintain between 800 ~ 1200mV by the add-on controlling sodium chlorate, obtain rich gold solution.
2. a kind of leaching method containing gold and copper in golden electron wastes according to claim 1, it is characterized in that, the particle diameter of described crushed particles is 1.49mm, and after ball-milling processing, particle diameter is 0.64mm.
3. a kind of leaching method containing gold and copper in golden electron wastes according to claim 1, is characterized in that, described step 3. in leaching liquid be the sulphuric acid soln of 150g/L, solid-to-liquid ratio is 1:8, and temperature of reaction is 80 DEG C, and the reaction times is 8h.
4. a kind of leaching method containing gold and copper in golden electron wastes according to claim 1, is characterized in that, described step 4. in leaching liquid be the sulphuric acid soln of 100g/L, solid-to-liquid ratio is 1:8, and temperature of reaction is 40 DEG C, and the reaction times is 90min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510311770.2A CN104894383A (en) | 2015-06-09 | 2015-06-09 | Leaching method of gold and copper in gold-contained electronic waste |
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| CN201510311770.2A CN104894383A (en) | 2015-06-09 | 2015-06-09 | Leaching method of gold and copper in gold-contained electronic waste |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105234160A (en) * | 2015-11-17 | 2016-01-13 | 成都移动魔方科技有限公司 | Automatic recovery method of electronic products |
| CN105234159A (en) * | 2015-11-17 | 2016-01-13 | 成都移动魔方科技有限公司 | Automatic recovery system of electronic products |
| CN105345476A (en) * | 2015-11-17 | 2016-02-24 | 成都移动魔方科技有限公司 | Automatic recycling device for electronic products |
| CN105861852A (en) * | 2016-03-04 | 2016-08-17 | 北京科技大学 | Cyaniding-free gold extraction method |
| CN107460324A (en) * | 2017-08-23 | 2017-12-12 | 中南大学 | A kind of method that silver anode slime control current potential prepares four or nine gold medals |
| CN107841630A (en) * | 2017-11-08 | 2018-03-27 | 东江环保股份有限公司 | Wiring board is high and low metal separation method |
| CN108977662A (en) * | 2018-07-13 | 2018-12-11 | 兰州金川新材料科技股份有限公司 | A method of cobalt chloride solution and copper-bath are prepared using ferro-cobalt |
| CN109848172A (en) * | 2018-12-26 | 2019-06-07 | 安徽万纬工程管理有限责任公司 | A kind of petrochemical industry refuse processing method |
| CN111057865A (en) * | 2020-01-06 | 2020-04-24 | 烟台市金奥环保科技有限公司 | Method for recovering gold and silver from high-arsenic gold concentrate |
| CN113528850A (en) * | 2021-07-26 | 2021-10-22 | 中南大学 | Method for purifying gold by controlling potential |
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| CN85106670A (en) * | 1985-08-31 | 1987-03-11 | 中国有色金属工业总公司昆明贵金属研究所 | Extract precious metal with the CONTROLLED POTENTIAL method from the anode sludge |
| CN104532005A (en) * | 2014-12-23 | 2015-04-22 | 清远市东江环保技术有限公司 | Resourceful comprehensive utilization method of waste printed circuit boards |
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2015
- 2015-06-09 CN CN201510311770.2A patent/CN104894383A/en active Pending
Patent Citations (2)
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| CN85106670A (en) * | 1985-08-31 | 1987-03-11 | 中国有色金属工业总公司昆明贵金属研究所 | Extract precious metal with the CONTROLLED POTENTIAL method from the anode sludge |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105234160A (en) * | 2015-11-17 | 2016-01-13 | 成都移动魔方科技有限公司 | Automatic recovery method of electronic products |
| CN105234159A (en) * | 2015-11-17 | 2016-01-13 | 成都移动魔方科技有限公司 | Automatic recovery system of electronic products |
| CN105345476A (en) * | 2015-11-17 | 2016-02-24 | 成都移动魔方科技有限公司 | Automatic recycling device for electronic products |
| CN105861852A (en) * | 2016-03-04 | 2016-08-17 | 北京科技大学 | Cyaniding-free gold extraction method |
| CN105861852B (en) * | 2016-03-04 | 2018-09-28 | 北京科技大学 | A method of without cyanidation gold-extracted |
| CN107460324A (en) * | 2017-08-23 | 2017-12-12 | 中南大学 | A kind of method that silver anode slime control current potential prepares four or nine gold medals |
| CN107841630A (en) * | 2017-11-08 | 2018-03-27 | 东江环保股份有限公司 | Wiring board is high and low metal separation method |
| CN107841630B (en) * | 2017-11-08 | 2019-05-10 | 东江环保股份有限公司 | Wiring board is high and low metal separation method |
| CN108977662A (en) * | 2018-07-13 | 2018-12-11 | 兰州金川新材料科技股份有限公司 | A method of cobalt chloride solution and copper-bath are prepared using ferro-cobalt |
| CN109848172A (en) * | 2018-12-26 | 2019-06-07 | 安徽万纬工程管理有限责任公司 | A kind of petrochemical industry refuse processing method |
| CN111057865A (en) * | 2020-01-06 | 2020-04-24 | 烟台市金奥环保科技有限公司 | Method for recovering gold and silver from high-arsenic gold concentrate |
| CN113528850A (en) * | 2021-07-26 | 2021-10-22 | 中南大学 | Method for purifying gold by controlling potential |
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