CN108950218A - A method of recycling gold, silver and copper from waste printed circuit board - Google Patents
A method of recycling gold, silver and copper from waste printed circuit board Download PDFInfo
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- CN108950218A CN108950218A CN201810921301.6A CN201810921301A CN108950218A CN 108950218 A CN108950218 A CN 108950218A CN 201810921301 A CN201810921301 A CN 201810921301A CN 108950218 A CN108950218 A CN 108950218A
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- copper
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- circuit board
- printed circuit
- waste printed
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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
- C22B11/046—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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- 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
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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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 method that the present invention relates to a kind of to recycle gold, silver and copper from waste printed circuit board, it include: to be crushed waste printed circuit board, furnace charge is obtained, puts into smelting furnace and calcines, obtain fused materials and clinker, sulfuric acid leaching is added in fused materials, leachate and leached mud is obtained by filtration, electrolysis copper processed is wherein carried out after leachate extracting copper, silver is made in raffinate electrolysis, chloroazotic acid is added in leached mud, and gold is obtained by extraction in acquired solution.The method of the invention process flow is short, practical, and gold, silver high-value product and copper are obtained from old circuit board, is particularly suitable for the waste printed circuit board raw material that copper content is higher than 20%, has environment protection significance outstanding and economic benefit.
Description
Technical field
The present invention relates to old circuit board resource recycling methods, especially a kind of to recycle from waste printed circuit board
The method of gold, silver and copper.
Background technique
The rapid development of China's electronics industry, electronic product update speed is fast, caused by generated electron wastes
Environmental problem is increasingly prominent.For example, China year scrap update household electrical appliances be more than 25,000,000, average annual growth 3%-5%, only this
One produced electronic waste estimates that the year two thousand twenty will be up to 100,000,000 tons.Waste printed circuit board (WPCBs) is in electronic waste
Common item, since containing there are many poisonous and harmful element, conventional method is difficult to handle, generally requires and remove from electronic device
Individually separately store.Waste printed circuit board is the solid waste by government regulation, is rich in a variety of precious metals, and easy to pollute
Environment studies its processing scheme with environment protection significance outstanding.
Printed wiring board is mainly made of substrate, electronic component and scolding tin three parts, and substrate is by high molecular polymer (tree
Rouge), glass fibre or brown paper and high-purity copper foil bond.Substrate is only the carrier of electronic component, each for supporting
The connection of kind electronic component, and electronic component is only the main body for realizing electronic apparatus various functions.There is research to computer main board point
Analysis discovery, electronic component, substrate and scolding tin three's proportion are about 58%, 37% and 5%.This is but also in printed circuit board
Usually contain about 40% metal, 30% plastics and 30% indissoluble oxide, almost contain institute in the periodic table of elements
There is common element.It is estimated that about 0.5k gold, 130k copper, 10k will be spent by averagely manufacturing the computer wiring board of 1t
Iron, 60k lead, 40k tin, 36k nickel and 40k antimony and the rare precious metals such as palladium and platinum.And only wherein the gold value of 0.5k is as high as
150000 yuan, the gold grade in significantly larger than general gold mine ore.Therefore, metal component is contamination-freely recycled from WPCBs Green
It recycles, the serious situation that China's metal resource relies on import for a long time can not only be alleviated to a certain extent, and have important
Economic results in society.
Patent application CN106519438A discloses a kind of waste printed circuit board/waste and old bumper reclaiming fender
The method of material after waste printed circuit board is removed metal material, crushes, is mixed together granulation, the party with waste and old bumper
Method first has to removing waste printed circuit board into metal material, and is only that this step is just difficult in practice, due to gold
Category is that the modes such as welding or printing combine in the circuit board, either manual demolition or long-time acid soak, is all difficult to
Realize preferable metal removal effect.And padded coaming market area tends to be saturated, and this method bring economic benefit is general.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that existing waste printed circuit board is reluctant, product market value
Low problem provides a kind of method that gold, silver and copper are recycled from waste printed circuit board.
Concrete scheme is as follows:
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge is obtained；
Step 2: by the resulting furnace charge investment smelting furnace of step 1, being calcined at 850-980 DEG C, obtain fused materials and furnace
Slag；
Step 3: sulfuric acid leaching is added into the fused materials that step 2 obtains, leachate and leached mud is obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, isolated organic phase and raffinate are described
Organic phase is stripped to obtain copper-bath, and silver is made in the raffinate electrolysis；
Step 5: chloroazotic acid is added in the resulting leached mud of step 3, gold is obtained by extraction in acquired solution；
Step 6: it is electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 40-150g/L,
Isolation film is set between anode region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, it is residual
Remaining solution is back to use the leaching process of fused materials in step 3.
Further, it is 1-100mm that the obtained furnace size is crushed in step 1.
Further, it is 1:0.001- that step 2, which includes: 2a by the resulting furnace charge of step 1 and additive according to mass ratio,
0.003 mixes, and obtains mixture charge, mixture charge is put into smelting furnace according to the speed of 50-200kg/h by 2b, at 850-950 DEG C
Calcining, obtains fused materials and clinker.
Further, additive described in step 2 is calcium oxide, sodium oxide molybdena, potassium oxide, silica, aluminium oxide, oxidation
At least one of iron, titanium oxide.
Further, the mass fraction of sulfuric acid is 60.0-98.3% in step 3, and the dosage of sulfuric acid is fused materials gross weight
5%-20%, leach 2-5h at room temperature.
Further, extractant A is M5640 in step 4, and extractant dosage is the 10-30% of leachate volume to be extracted；
Optional, back extraction uses concentration for the dilute sulfuric acid of 1-10g/L in step 4.
Further, the dosage of chloroazotic acid is 2-3 times of the leached mud gross weight in step 5；
Optional, golden component will be contained including addition extractant B by, which extracting in step 5, is transferred to extraction phase, addition back extraction later
Agent is taken to obtain gold.
Further, extraction uses extractant B in diethylene glycol dibutyl ether, methylisobutylketone or butylphosphoric acid ester in step 5
Any one, uses strippant for oxalic acid or sodium nitrite.
Further, the temperature of the extraction system or back extraction system that extract in step 5 is 20-40 DEG C；
Optional, the mode that copper ion concentration adjusts in step 6 includes dilution, precipitating or crystallization.
The present invention also protects the method for recycling gold, silver and copper from waste printed circuit board with described, is prepared
Gold, silver or copper.
The utility model has the advantages that
In the present invention, it is sent directly into smelting furnace after waste printed circuit board is crushed, by smelting furnace hot environment, waste and old line
Organic principle full combustion in the plate of road, by controlling the reaction temperature of smelting furnace, so that the organic principle in old circuit board turns
Clean flue gas is turned to, the generation of the pernicious gases such as dioxin is avoided.
Moreover the organic principle burning in old circuit board discharges a large amount of thermal energy, helps the metal in old circuit board
Ingredient dissolution reduces smelting furnace to 30% or so of extraneous energy demand total amount, reduces the energy consumption of entire technique.
Further, contain gold, silver and copper in smelting furnace in molten product, dystectic element such as platinum and palladium then enters furnace
Slag realizes the initial gross separation of valuable metals in waste circuit board with the separation of fused materials and clinker, solves your traditional gold
Belong to the problem that the separation of palladium-silver present in separation is interfered, platinum and gold separation are difficult.
The present invention obtains the higher golden simple substance of purity by extracting and being stripped technology, improves the value of product, has
Preferable economic benefit.
In short, the method for the invention process flow is short, practical, gold, silver high value is obtained from old circuit board
Product and copper, be particularly suitable for copper content be higher than 20% waste printed circuit board raw material, have environment protection significance outstanding and
Economic benefit.
Specific embodiment
The definition of part term used in the present invention is given below, other terms that do not address have well known in the art
Definition and meaning:
Waste printed circuit board, also known as discarded printed circuit boards are the supporter and electronic component electricity of electronic component
The carrier of gas connection.In the present invention waste printed circuit board include common household electrical appliance, mobile device, control unit equipment,
The printed wiring board that the recycling such as computer obtain, the printed wiring board remove the impurity such as dust merely through simple cleaning treatment,
Without the fractionation of metal structure and the dismounting of electronic component.
It is 1-100mm, preferably 50-95mm that the obtained furnace size is crushed in step 1 of the present invention, more preferably
60-80mm, such as 65mm, such as 70mm, such as 75mm.Undersized be easy to cause smelting furnace fouling, and granularity is compared higher than 50mm
Lower granularity is not susceptible to furnace charge reunion.
Waste printed circuit board is calcined in smelting furnace in the present invention, is preferably added to a certain amount of additive auxiliary calcining, is added
Agent is added to be preferably at least one of calcium oxide, sodium oxide molybdena, potassium oxide, silica, aluminium oxide, iron oxide or titanium oxide, more preferably
Calcium oxide and silica mixing or sodium oxide molybdena and silica mixing, mixed proportion can be 1:1 or 1:2, additive
The slag wall built-up in softening clinker, reduction smelting furnace, which is added, has preferable effect.It should be noted that the silica include SiO,
SiO2And Si2O6。
In step 2 of the present invention, smelting furnace calcination temperature needs to control at 850-980 DEG C, is lower than 850 DEG C, dioxin etc. has
Evil gas decomposition is not thorough.Higher than 980 DEG C, copper can bring more noble metals into and enter in fused materials, increase subsequent noble metal
Separating difficulty.Preferred 850-950 DEG C of temperature of smelting furnace, 850 DEG C or more, the pernicious gases such as dioxin can be completely broken down, gained
Flue gas can be emptied by conventional dust removal, reduce fume treatment burden and cost.With smelting furnace calcination temperature relationship it is biggish be into
Expect speed, mixture charge preferably incorporates smelting furnace according to the speed of 50-200kg/h, is lower than 50kg/h, and smelting furnace production efficiency is low, place
It is slow to manage speed, is higher than 200kg/h, the material calcining that early period enters is incomplete, is not only easy freezing of a furnace, but also under metal recovery rate
Drop.The noble metals such as platinum, palladium are usually contained in clinker, can be sent to relevant treatment unit and further be recycled valuable metal.
The mass fraction of sulfuric acid is 60.0-98.3% in step 3 of the present invention, and the dosage of sulfuric acid is fused materials gross weight
5%-20% leaches 2-5h at room temperature.Sulfuric acid concentration is lower than 60.0%, since copper leaches a large amount of acid of consumption first, silver-colored leaching
It is insufficient.20% of sulfuric acid dosage more than fused materials gross weight can interfere extraction process, increase extraction and separation difficulty.
Raffinate is electrolysed in step 4 of the present invention, obtains silver, and electrolysis mode uses existing conventional method, such as
Under 1.5~3.5 volts of direct current electro ultrafiltrations, silver is deposited on cathode on cathode with loose large particle crystal shape, collects the silver of deposition
Obtain product.
Organic phase described in step 4 of the present invention is stripped to obtain copper-bath, it is preferable that back extraction uses concentration for 1-
The dilute sulfuric acid of 10g/L has preferable back extraction efficiency, it is highly preferred that using concentration for the dilute sulfuric acid of 3-6g/L, favorably at this time
The progress of copper-bath electrolytic process in step 6.
Chloroazotic acid is added in leached mud in step 5 of the present invention, by Gold leaching, into liquid phase, after being acted on by extractant, into having
In machine extraction phase, it is stabilized in extraction phase with the compound form of gold.By the back extraction aqueous solvent of reproducibility, so that
The compound of gold is converted into golden simple substance and is precipitated.Chloroazotic acid is by concentrated hydrochloric acid (HCl) and concentrated nitric acid (HNO3) it is by volume 3:1 group
At.Preferably, extractant is any one in diethylene glycol dibutyl ether, methylisobutylketone or butylphosphoric acid ester, and strippant is oxalic acid
Or sodium nitrite.The extraction system of extraction or the temperature for being stripped system are 20-40 DEG C, not only result in extraction higher than 40 DEG C
Take agent or the volatilization of strippant, it is often more important that will cause the decline of golden simple substance purity, it may be possible to make since temperature raises
It is increased at the resulting solution system oxidisability of leached mud, more impurity components are leached, and are precipitated during back extraction.
In step 6 of the present invention, the copper ion concentration in copper-bath is adjusted to 40-150g/L, is electrolysed later.It needs
It is noted that adjustment mode includes but is not limited to dilute, precipitate or crystallize, make in electrolytic process after adjustment, copper ion
It being precipitated to the maximum extent in cathode, the electrochemical reaction of anode region will not both consume the valuable element other than the copper in solution,
The valence state or existence form that the valuable element other than the copper in solution will not be destroyed, for example, anode region only consumes water
Or hydroxide ion.Terminate to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, residual solution is back to use step 3
The leaching process of middle fused materials.It, could will be in solution it should be noted that isolation film is arranged between anode region and cathodic region
Copper ion concentration be electrolysed to≤30g/L, while residual solution acid concentration with higher, the leaching of fused materials can be back to use
Process out.Isolation film preferably ceramic film or PP film can be resistant to the acidity and corrosivity of electrolysis system, when avoiding continued electrolysis
Wear film breakage.
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.It is real
It applies and particular technique or condition person is not specified in example, according to the literature in the art described technology or conditions or according to product
Specification carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.Under
In the embodiment in face, such as it is not known and illustrates, " % " refers both to weight percent.
Contain in waste printed circuit board in embodiment: plastics 49.62%, copper 20.54%, iron 7.46%, bromide
4.65%, lead 4.08%, tin 3.26%, nickel 3.18%, antimony 1.83%, zinc 0.47%, gold 0.12%, silver-colored 0.16%, cadmium
0.06%, palladium 0.03%, cobalt 0.02%, platinum 0.01%, mercury 0.002%, surplus other elements content are lower than 0.002%.
Embodiment 1
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge, granularity 55-65mm are obtained；
Step 2: according to mass ratio it is that 1:0.002 is mixed by the resulting furnace charge of step 1 and additive, obtains mixture charge,
By mixture charge according in the speed investment smelting furnace of 100kg/h, is calcined at 850 DEG C, obtain fused materials and clinker；Additive
For calcium oxide；
Step 3: 68% sulfuric acid of mass fraction being added into the fused materials that step 2 obtains, dosage is fused materials gross weight
15%, leach 3h at room temperature, leachate and leached mud be obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, extractant A close Kang Pu chemical industry of attaching most importance to has
The M5640 that limit company provides, dosage are the 20% of leachate volume to be extracted, and isolated organic phase and raffinate are described to have
Copper-bath is obtained by extraction in machine on the contrary, and back extraction uses concentration for the dilute sulfuric acid of 3g/L；Silver, silver is made in the raffinate electrolysis
It is precipitated in cathode, collection obtains silver-colored simple substance, purity 99.82%, the rate of recovery 99.3%；
Step 5: the resulting leached mud of step 3 being added in chloroazotic acid at room temperature, is filtered after reacting 3h, is removed obtained by solid phase
Diethylene glycol dibutyl ether is added in solution, is extracted, organic phase is separated, matter is added into the organic phase being obtained by extraction at room temperature
The sodium nitrite solution that amount score is 25%, is stirred, and is stood, and precipitate is arranged at solution bottom, is washed after filtering, is dried to obtain golden list
Matter, purity 99.95%, the rate of recovery 99.0%；
Step 6: being electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 65g/L, in sun
Ceramic membrane is set between polar region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, purity is
99.99%, the rate of recovery 99.1%, residual solution is back to use the leaching process of fused materials in step 3.
Embodiment 2
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge, granularity 30-50mm are obtained；
Step 2: according to mass ratio it is that 1:0.001 is mixed by the resulting furnace charge of step 1 and additive, obtains mixture charge,
By mixture charge according in the speed investment smelting furnace of 150kg/h, is calcined at 920 DEG C, obtain fused materials and clinker；Additive
It according to mass ratio is that 1:2 is mixed for calcium oxide and sodium oxide molybdena；
Step 3: 72% sulfuric acid of mass fraction being added into the fused materials that step 2 obtains, dosage is fused materials gross weight
10%, leach 4h at room temperature, leachate and leached mud be obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, extractant A close Kang Pu chemical industry of attaching most importance to has
The M5640 that limit company provides, dosage are the 17% of leachate volume to be extracted, and isolated organic phase and raffinate are described to have
Copper-bath is obtained by extraction in machine on the contrary, and back extraction uses concentration for the dilute sulfuric acid of 8g/L；Silver, silver is made in the raffinate electrolysis
It is precipitated in cathode, collection obtains silver-colored simple substance, purity 99.65%, the rate of recovery 99.2%；
Step 5: the resulting leached mud of step 3 being added in chloroazotic acid at room temperature, is filtered after reacting 3h, is removed obtained by solid phase
Methylisobutylketone is added in solution, is extracted, organic phase is separated, quality is added into the organic phase being obtained by extraction at room temperature
The sodium nitrite solution that score is 15% stirs, and stands, and precipitate is arranged at solution bottom, washes after filtering, is dried to obtain golden list
Matter, purity 99.94%, the rate of recovery 99.2%；
Step 6: being electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 85g/L, in sun
Ceramic membrane is set between polar region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, purity is
99.99%, the rate of recovery 99.0%, residual solution is back to use the leaching process of fused materials in step 3.
Embodiment 3
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge, granularity 70-95mm are obtained；
Step 2: the resulting furnace charge of step 1 and additive are mixed according to mass ratio for 0.003, mixture charge is obtained, it will
Mixture charge is calcined at 905 DEG C according in the speed investment smelting furnace of 170kg/h, obtains fused materials and clinker；Additive is
Silica；
Step 3: 80% sulfuric acid of mass fraction being added into the fused materials that step 2 obtains, dosage is fused materials gross weight
6%, leach 5h at room temperature, leachate and leached mud be obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, extractant A close Kang Pu chemical industry of attaching most importance to has
The M5640 that limit company provides, dosage are the 30% of leachate volume to be extracted, and isolated organic phase and raffinate are described to have
Copper-bath is obtained by extraction in machine on the contrary, and back extraction uses concentration for the dilute sulfuric acid of 5g/L；Silver, silver is made in the raffinate electrolysis
It is precipitated in cathode, collection obtains silver-colored simple substance, purity 99.85%, the rate of recovery 99.5%；
Step 5: the resulting leached mud of step 3 being added in chloroazotic acid at room temperature, is filtered after reacting 3h, is removed obtained by solid phase
Butylphosphoric acid ester is added in solution, is extracted, organic phase is separated, oxalic acid is added into the organic phase being obtained by extraction at room temperature,
Stirring is stood, and there is precipitate in solution bottom, washes after filtering, is dried to obtain golden simple substance, purity 99.98%, the rate of recovery is
99.6%；
Step 6: it is electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 120g/L,
Ceramic membrane is set between anode region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper, purity in cathode
It is 99.99%, the rate of recovery 99.3%, residual solution is back to use the leaching process of fused materials in step 3.
Embodiment 4
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge, granularity 50-100mm are obtained；
Step 2: the resulting furnace charge of step 1 and additive are mixed according to mass ratio for 0.003, mixture charge is obtained, it will
Mixture charge is calcined at 980 DEG C according in the speed investment smelting furnace of 200kg/h, obtains fused materials and clinker；Additive is
Calcium oxide and aluminium oxide are mixed according to mass ratio 1:1；
Step 3: 98.3% sulfuric acid of mass fraction being added into the fused materials that step 2 obtains, dosage is that fused materials are total
The 5% of weight, leaches 2h at room temperature, and leachate and leached mud is obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, extractant A close Kang Pu chemical industry of attaching most importance to has
The M5640 that limit company provides, dosage are the 10% of leachate volume to be extracted, and isolated organic phase and raffinate are described to have
Copper-bath is obtained by extraction in machine on the contrary, and back extraction uses concentration for the dilute sulfuric acid of 1g/L；Silver, silver is made in the raffinate electrolysis
It is precipitated in cathode, collection obtains silver-colored simple substance, purity 99.71%, the rate of recovery 99.3%；
Step 5: the resulting leached mud of step 3 being added in chloroazotic acid at room temperature, is filtered after reacting 3h, is removed obtained by solid phase
Diethylene glycol dibutyl ether is added in solution, is extracted, organic phase is separated, grass is added into the organic phase being obtained by extraction at room temperature
Acid stirs, and stands, there is precipitate in solution bottom, washes after filtering, is dried to obtain golden simple substance, purity 99.98%, the rate of recovery
It is 99.6%；
Step 6: it is electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 150g/L,
Ceramic membrane is set between anode region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper, purity in cathode
It is 99.99%, the rate of recovery 99.2%, residual solution is back to use the leaching process of fused materials in step 3.
Embodiment 5
A method of recycling gold, silver and copper from waste printed circuit board, comprising the following steps:
Step 1: waste printed circuit board being crushed, furnace charge, granularity 1-50mm are obtained；
Step 2: according to mass ratio it is that 1:0.001 is mixed by the resulting furnace charge of step 1 and additive, obtains mixture charge,
By mixture charge according in the speed investment smelting furnace of 50kg/h, is calcined at 860 DEG C, obtain fused materials and clinker；Additive
It is mixed for calcium oxide and silica according to mass ratio 1:1；
Step 3: 60% sulfuric acid of mass fraction being added into the fused materials that step 2 obtains, dosage is fused materials gross weight
20%, leach 2h at room temperature, leachate and leached mud be obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, extractant A close Kang Pu chemical industry of attaching most importance to has
The M5640 that limit company provides, dosage are the 10% of leachate volume to be extracted, and isolated organic phase and raffinate are described to have
Copper-bath is obtained by extraction in machine on the contrary, and back extraction uses concentration for the dilute sulfuric acid of 10g/L；Silver is made in the raffinate electrolysis,
Silver is precipitated in cathode, and collection obtains silver-colored simple substance, purity 99.50%, the rate of recovery 99.0%；
Step 5: the resulting leached mud of step 3 being added in chloroazotic acid at room temperature, is filtered after reacting 3h, is removed obtained by solid phase
Diethylene glycol dibutyl ether is added in solution, is extracted, organic phase is separated, matter is added into the organic phase being obtained by extraction at room temperature
The sodium nitrite solution that amount score is 20%, is stirred, and is stood, and precipitate is arranged at solution bottom, is washed after filtering, is dried to obtain golden list
Matter, purity 99.94%, the rate of recovery 99.2%；
Step 6: being electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 40g/L, in sun
Ceramic membrane is set between polar region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, purity is
99.99%, the rate of recovery 99.5%, residual solution is back to use the leaching process of fused materials in step 3.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: the following steps are included:
Step 1: waste printed circuit board being crushed, furnace charge is obtained；
Step 2: by the resulting furnace charge investment smelting furnace of step 1, being calcined at 850-980 DEG C, obtain fused materials and clinker；
Step 3: sulfuric acid leaching is added into the fused materials that step 2 obtains, leachate and leached mud is obtained by filtration；
Step 4: by step 3 resulting leachate extractant A extracting copper, isolated organic phase and raffinate are described organic
Copper-bath is obtained by extraction on the contrary, silver is made in the raffinate electrolysis；
Step 5: chloroazotic acid is added in the resulting leached mud of step 3, gold is obtained by extraction in acquired solution；
Step 6: being electrolysed after the copper ion concentration in the resulting copper-bath of step 4 is adjusted to 40-150g/L, in sun
Isolation film is set between polar region and cathodic region, terminates to be electrolysed as copper ion concentration≤30g/L, obtains copper in cathode, it is remaining molten
Liquid is back to use the leaching process of fused materials in step 3.
2. the method according to claim 1 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
It is 1-100mm that the obtained furnace size is crushed in rapid 1.
3. the method according to claim 1 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
Rapid 2 include: 2a by the resulting furnace charge of step 1 and additive according to mass ratio be that 1:0.001-0.003 is mixed, and obtains holding furnace
Material, 2b by mixture charge according to 50-200kg/h speed put into smelting furnace, calcined at 850-950 DEG C, obtain fused materials and
Clinker.
4. the method according to claim 3 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
Additive described in rapid 2 is at least one of calcium oxide, sodium oxide molybdena, potassium oxide, silica, aluminium oxide, iron oxide or titanium oxide.
5. the method according to claim 1 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
The mass fraction of sulfuric acid is 60.0-98.3% in rapid 3, and the dosage of sulfuric acid is the 5%-20% of fused materials gross weight, is soaked at room temperature
2-5h out.
6. the method according to claim 1 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
Extractant A is M5640 in rapid 4, and extractant dosage is the 10-30% of leachate volume to be extracted；Optional, it is stripped in step 4
Take the dilute sulfuric acid for using concentration as 1-10g/L.
7. the method according to claim 1 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
The dosage of chloroazotic acid is 2-3 times of the leached mud gross weight in rapid 5；
Optional, golden component will be contained including addition extractant B by, which extracting in step 5, is transferred to extraction phase, adds strippant later
Obtain gold.
8. the method according to claim 7 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
Extraction uses extractant B for any one in diethylene glycol dibutyl ether, methylisobutylketone or butylphosphoric acid ester in rapid 5, using back extraction
Agent is oxalic acid or sodium nitrite.
9. the method according to claim 7 for recycling gold, silver and copper from waste printed circuit board, it is characterised in that: step
The temperature of the extraction system or back extraction system that extract in rapid 5 is 20-40 DEG C；
Optional, the mode that copper ion concentration adjusts in step 6 includes dilution, precipitating or crystallization.
10. with the method for any of claims 1-9 for recycling gold, silver and copper from waste printed circuit board, system
Standby obtained gold, silver or copper.
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Application publication date: 20181207 |