CN104264184A - Method for extracting metallic copper from waste circuit board - Google Patents
Method for extracting metallic copper from waste circuit board Download PDFInfo
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- CN104264184A CN104264184A CN201410463322.XA CN201410463322A CN104264184A CN 104264184 A CN104264184 A CN 104264184A CN 201410463322 A CN201410463322 A CN 201410463322A CN 104264184 A CN104264184 A CN 104264184A
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- 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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- 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
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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
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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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
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Abstract
The invention discloses a method for extracting metallic copper from a waste circuit board. The method comprises the following steps: firstly, crushing the waste circuit board from which elements and parts are removed into blocks, crushing by virtue of a crusher, and sieving by a 30-mesh sieve; sequentially carrying out winnowing and electric separation on the obtained granular powder to obtain a metal concentrate with relatively high copper content; leaching copper ions from the metal concentrate by using a leaching agent water solution which is composed of sodium chlorate, sulfuric acid and water; removing solid substances from the obtained leaching liquid by centrifugal separation or filter press filtration; carrying out five-stage extraction and second-stage reverse extraction on the obtained filtrate to obtain a copper-enriched solution, carrying out electrodeposition on the obtained copper-enrich solution by virtue of an electrode method, thus finally obtaining copper of which the purity is over 99.99% on the cathode material, so as to finish extraction of the metallic copper from the waste circuit board. According to the method disclosed by the invention, the metallic copper can be efficiently extracted from the waste circuit board; the method has the technical characteristics of high efficiency, energy saving, low cost, simple process and the like and is capable of achieving recycling and innocent treatment of the waste circuit board.
Description
Technical field
The invention belongs to technical field of environmental science, relate to the treatment process of electron wastes in solid waste, particularly a kind of method extracting metallic copper from old circuit board, to realize, old circuit board is innoxious, recycling.
Background technology
Printed-wiring board (PWB) is the supporter of electronic devices and components electrical connection in electric equipment products.More and more be eliminated along with the quickening of various electric equipment products update speed.If these old circuit boards are simply discarded, the heavy metal in wiring board and the macromolecular material on substrate produce huge pollution by surrounding environment, and the valuable metal simultaneously in old circuit board is not recovered and causes waste.Adopt suitable recovery and utilization technology to recycle old circuit board, can not only secondary pollution be avoided, good economic benefit can also be brought.
The purification technique of metal in old circuit board, mainly contains wet method, pyrogenic process, biological process and other treatment technologies.
The acid treatment old circuit board of wet method strong oxidizing property, changes into metal ion by metal oxygen wherein and enters into solution, adopts displacement or electrolysis treatment technique Footwall drift after purifying.This treatment process nitric acid etc., as strong oxidizer, can discharge a large amount of NOx, contaminate environment in treating processes, and have a large amount of producing containing heavy metal waste liquid, if deal with improperly, easily cause secondary pollution.
Pyrogenic process old circuit board is put into smelting furnace burn, and adopts the precious metal in pyrogenic process and electrolytic process recovery lime-ash after the components such as resin being removed again.The method can produce a large amount of poison gas containing dioxin, furans and polychlorinated biphenyl material, there is secondary pollution and potential safety hazard.
Biological process utilizes the process of consumption of microorganism to special metal to be extracted from old circuit board by metal.The method technique is simple, working cost is low, easy and simple to handle, but the cultivation fee of microorganism is comparatively large and maturity is lower, and the treatment time is general longer simultaneously.
Other treatment processs are generally just in the method for conceptual phase, and ubiquity expense is large, occupation of land is wide, be unsuitable for shortcomings such as applying.
Wet method and and pyrogenic process technology be metallic ore smelt basis on grow up, technology is comparatively ripe, and cost is also lower, and Footwall drift purity is higher.Relative to pyrogenic process, although wet method must consume the leaching that a large amount of chemical reagent carries out metal, technique is simply ripe, and do not produce a large amount of toxic and harmfuls, energy consumption is less, operates the pollution that suitably can greatly reduce environment.For wet method, the key problem in technology of the extraction of copper is mainly in the leaching of copper and extract the purity problem etc. of copper.At present, the leaching copper system of application great majority are all made up of the oxygenant of copper and complexing agent, and metallic copper is become cupric ion by oxygenant, and cupric ion generates complex compound with complexing agent again, realizes the dissolving of copper.But the problem that the leaching yield of ubiquity copper is not high and conventional leaching copper system main component is nitric acid, the reaction of leaching copper can discharge a large amount of NOx contaminate environment.Meanwhile, the subsequent technique of the leaching of copper is the selective extraction of copper, and for copper extraction process, acidity and strong oxidizer are the biggest obstacles of copper extractant.In the extraction process of copper, generally need material liquid pH >1.2, or sulfuric acid concentration C
sulfuric acid<20g/L, but during extractive reaction, often extract 1gCu releasing 1.54g sulfuric acid.Suppose stock liquid pH=7 or C
sulfuric acid=0, in extraction process, as feed liquid C
sulfuric acidduring=20g/L, extract C
copper=13g/L.So far, copper can not being extracted again, and therefore, when not regulating pH, stock liquid C need be made
copper<13g/L as well.And simultaneously, the leaching of copper generally need add a large amount of acid, make original liquid acidity very large, i.e. pH<1.2, therefore, be difficult to normally extract copper when not adjust ph.In addition, extract extraction agent used and be very easily oxidized by strong oxidizer and lost efficacy, but generally can add the strong oxidizers such as nitric acid during Leaching reaction, therefore very easily cause the inefficacy of extraction agent to lose.In addition, extraction process substitutes into that the impurity of rich copper liquid is too high and to make the purity of cathode copper not high be also the ubiquitous problem of wet method.
Summary of the invention
The object of the invention is the not high and release NOx of leaching yield in order to solve copper in wet-milling processing process on environment and leach liquor acidity too high and affect extractive reaction and strong oxidizer and extraction agent can be made to lose efficacy and the cathode copper purity that extracts not high-technology problem and provide a kind of method extracting metallic copper from old circuit board; the method realizes the resource utilization recycling of old circuit board; economize on resources, protection of the environment.
Technical scheme of the present invention
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk that weight is preferably 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
(2), the leaching of cupric ion
Sodium chlorate, the vitriol oil and water are carried out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.05-0.5mol/L, and sulfuric acid concentration is 0.1 ~ 5mol/L;
Join in reactor by the leaching agent aqueous solution, then add the metal concentrate that step (1) obtains, then controlling temperature of reaction kettle is 20-80 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 0.5-3.0h, obtains copper leach liquor after reaction terminates;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
Concrete Leaching mechanism is shown below:
NaClO
3+3H
2SO
4+3Cu
3CuSO
4 + NaCl + 3H
2O （1）
Above-mentioned reactor used is titanium reactor or the ceramic reactor of temperature controllable;
(3), solid-liquid separation
The copper leach liquor of step (2) gained removes solid matter through centrifugation or Filter Press, obtains filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains rich copper liquid;
Described five grades extraction, namely at normal temperatures, with organic extractant continuous extraction 5 times, selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, in each extraction process organic extractant and leach liquor be in a ratio of 1 ︰ 4 ~ 4 ︰ 1, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that lix984, N910 or DZ973N and 26# kerosene calculate according to volume percent, and namely lix984, N910 or DZ973N:26# kerosene is that the ratio of 10 ~ 30%:70 ~ 90% mixes;
Described secondary back extraction, the copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures; In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 4 ~ 4 ︰ 1, and after back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
The sulphuric acid soln of described strip liquor to be concentration be 1 ~ 5mol/L;
The reaction process that above-mentioned extraction and back-extraction is got is shown below:
Extractive reaction is:
2RH（org）+ Cu
2+（aq）= CuR
2（org）+ 2H
+ （2）
Reextraction reaction is:
CuR
2（org）+ 2H
+（aq）= 2RH（org）+ Cu
2+ （3）
In formula: RH is organic extractant, CuR
2for extracted species, (aq) represents aqueous phase, and (org) represents organic phase;
Send into electrodeposition pond and carry out electrodeposition;
(5), electrodeposition carries copper
The rich copper liquid of step (4) gained is put into electrodeposition pond, spreading a layer thickness above rich copper liquid is that the PVC ball of 2 ~ 5mm is in order to absorb the irritant gas of releasing in electrolytic deposition process, the particle diameter of PVC ball is 2 ~ 5mm, cathode material adopts titanium plate, stainless steel plate or fine copper plate, anode material adopts lead-calcium-tin alloy plate, control flume voltage is 1.5 ~ 4.5V, and interpole gap is 2 ~ 16cm, and current density is 50 ~ 700A/m
2, temperature is 20 ~ 60 DEG C and carries out electrodeposition 0.5 ~ 10h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, thus completes the extraction of metallic copper in old circuit board;
In electrodeposition pond, the electrolytic deposition process of rich copper liquid is shown below:
Cathodic reaction:
Cu
2+ + 2e = Cu （4）
Anodic reaction is:
4OH
- = O
2 + 2H
2O + 4e （5）
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained is back in strip liquor, continues the copper of stripping in copper-loaded organic phase.
Beneficial effect of the present invention
A kind of method extracting metallic copper from old circuit board of the present invention, first, owing to adopting the solution that is made up of sodium chlorate, sulfuric acid and water as the leaching agent aqueous solution of copper, and avoid using the strong oxidizers such as nitric acid, therefore soak copper process can not produce NOx and cause pollution to environment, and the leaching yield of copper can reach 100%; Secondly, the acid used in leaching copper process less and in reaction process acid be consumed, therefore the acidity of the leach liquor of copper is very low, pH>1.2, can not cause negative impact to follow-up extractive reaction; Again, soak in the copper leach liquor of gained in copper process and there is no a large amount of strong oxidizers, thus the activity can not destroying organic extractant makes it to lose efficacy.
Further, a kind of method extracting metallic copper from old circuit board of the present invention, the copper leach liquor of gained obtains rich copper liquid through five grades extraction, two-stage back extraction, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continue to serve as the leaching of copper, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing; After this process makes to strip, in the rich copper liquid that obtains, the foreign matter content such as iron ion is less than below 2g/L, and the purity of the cathode copper that electrodeposition is obtained, more than 99.99%, achieves the resource utilization of old circuit board, minimizing, innoxious.
specific implementation method
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
Raw material used in various embodiments of the present invention or reagent are except following specified otherwise, and other are commercially available.
Lix984, Rui Pu novel material company limited of Liyang City produces;
N910, Tian Li chemical plant, Jingjiang City produces;
DZ973N, Zhengzhou German public chemical reagent factory is produced;
embodiment 1
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 300g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.05mol/L, and sulfuric acid concentration is 0.1mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 3.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
After back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that DZ973N and 26# kerosene calculates according to volume percent, namely DZ973N:26# kerosene is that the ratio of 30%:70% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 4, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 4 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 1mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 2mm is spread above rich copper liquid, the particle diameter of PVC ball is 2mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 4.5V, interpole gap is 16cm, and current density is 50A/m
2, temperature is 20 DEG C and carries out electrodeposition 0.5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 2
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 350g sodium chlorate and the 0.8L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.5mol/L, and sulfuric acid concentration is 5mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 0.5h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
By the filtrate of step (3) gained through five grades extraction, secondary back extraction, obtain the rich copper liquid that copper concentration is 40g/L, raffinate returns and continues to serve as leaching copper system;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that DZ973N and 26# kerosene calculates according to volume percent, namely DZ973N:26# kerosene is that the ratio of 10%:90% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 4 ︰ 1, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 4;
The aqueous sulfuric acid of described strip liquor to be concentration be 5mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 5mm is spread above rich copper liquid, the particle diameter of PVC ball is 5mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 1.5V, interpole gap is 2cm, and current density is 700A/m
2, temperature is 60 DEG C and carries out electrodeposition 10h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 3
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then the particle powder about 30 orders is shattered into pulverizer, then selection by winnowing is carried out, metallic particles is separated with non-metallic particle, to improve the content of metal, then carry out the part iron in electric separation removal mixed metal particles, to improve the purity leaching copper, thus obtain the higher metal concentrate of metal content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 250g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.3mol/L, and sulfuric acid concentration is 2mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 1.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that DZ973N and 26# kerosene calculates according to volume percent, namely DZ973N:26# kerosene is that the ratio of 20%:80% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 1, and extractive reaction carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 3mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 3mm is spread above rich copper liquid, the particle diameter of PVC ball is 3mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 3.2V, interpole gap is 10cm, and current density is 350A/m
2, temperature is 30 DEG C and carries out electrodeposition 5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 4
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 300g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.05mol/L, and sulfuric acid concentration is 0.1mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 3.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that lix984 and 26# kerosene calculates according to volume percent, namely lix984:26# kerosene is that the ratio of 30%:70% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 4, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 4 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 1mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 2mm is spread above rich copper liquid, the particle diameter of PVC ball is 2mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 4.5V, interpole gap is 16cm, and current density is 50A/m
2, temperature is 20 DEG C and carries out electrodeposition 0.5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 5
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 350g sodium chlorate and the 0.8L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.5mol/L, and sulfuric acid concentration is 5mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 0.5h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that lix984 and 26# kerosene calculates according to volume percent, namely lix984:26# kerosene is that the ratio of 10%:90% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 4 ︰ 1, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 4;
The aqueous sulfuric acid of described strip liquor to be concentration be 5mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 5mm is spread above rich copper liquid, the particle diameter of PVC ball is 5mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 1.5V, interpole gap is 2cm, and current density is 700A/m
2, temperature is 60 DEG C and carries out electrodeposition 10h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 6
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 250g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.3mol/L, and sulfuric acid concentration is 2mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 1.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that lix984 and 26# kerosene calculates according to volume percent, namely lix984:26# kerosene is that the ratio of 20%:80% mixes, in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 1, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 3mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 3mm is spread above rich copper liquid, the particle diameter of PVC ball is 3mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 3.2V, interpole gap is 10cm, and current density is 350A/m
2, temperature is 30 DEG C and carries out electrodeposition 5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 7
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 300g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.05mol/L, and sulfuric acid concentration is 0.1mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 3.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that N910 and 26# kerosene calculates according to volume percent, and namely N910:26# kerosene is that the ratio of 30%:70% mixes, and in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 4, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 4 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 1mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 2mm is spread above rich copper liquid, the particle diameter of PVC ball is 2mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 4.5V, interpole gap is 16cm, and current density is 50A/m
2, temperature is 20 DEG C and carries out electrodeposition 0.5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 8
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 350g sodium chlorate and the 0.8L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.5mol/L, and sulfuric acid concentration is 5mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 0.5h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that N910 and 26# kerosene calculates according to volume percent, and namely N910:26# kerosene is that the ratio of 10%:90% mixes, and in each extraction process, the volume ratio of organic extractant and leach liquor is 4 ︰ 1, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain rich copper liquid, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 4;
The aqueous sulfuric acid of described strip liquor to be concentration be 5mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 5mm is spread above rich copper liquid, the particle diameter of PVC ball is 5mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 1.5V, interpole gap is 2cm, and current density is 700A/m
2, temperature is 60 DEG C and carries out electrodeposition 10h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
embodiment 9
From old circuit board, extract a method for metallic copper, comprise the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into the bulk of 3 kilograms, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
In the metal concentrate obtained, count by weight percentage, wherein each metal content is: Cu 75%, Fe 7.5%, Al 2.1%, Pb 2.7%, Zn 0.7%, Mn 0.1%, Ag+As+Au+Ba+K+Li+Na+Ni is less than 0.1%, and surplus is nonmetallic ingredient;
(2), the leaching of cupric ion
First in titanium reactor, add 10L water, add 250g sodium chlorate and the 0.3L vitriol oil in the process then stirred, carry out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.3mol/L, and sulfuric acid concentration is 2mol/L;
Then join in reactor by the metal concentrate that 400g step (1) obtains, control temperature is 60 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 1.0h, obtains copper leach liquor;
Above-mentioned Leaching reaction makes the copper in metal concentrate and sodium chlorate react in acid system, generates cupric ion, realizes the leaching of cupric ion;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
By the copper leach liquor of step (2) gained plate-and-frame filter press solids removed by filtration insoluble substance, obtain filtrate;
(4), cupric ion is purified
After step (3) being filtered, the filtrate of gained is through five grades extraction, secondary back extraction, obtains the rich copper liquid that copper concentration is 40g/L;
Described five grades extraction, namely use organic extractant continuous extraction 5 times, the selective copper in filtrate is extracted in organic extractant, obtain copper-loaded organic phase, after five grades extraction, the raffinate of gained turns back in the leaching agent aqueous solution, continues to serve as the leaching of cupric ion;
Described organic extractant is that N910 and 26# kerosene calculates according to volume percent, and namely N910:26# kerosene is that the ratio of 20%:80% mixes, and in each extraction process, the volume ratio of organic extractant and leach liquor is 1 ︰ 1, and extraction process carries out at normal temperatures;
Described secondary back extraction, copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, obtain the rich copper liquid that copper concentration is 40g/L, after secondary back extraction, the organic phase of the remnants of gained is back in organic extractant after three grades of pickling, extracts the copper in leach liquor for continuing;
In each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 3mol/L;
(5), electrodeposition carries copper
Be that the rich copper liquid of 40g/L puts into electrodeposition pond by the copper concentration of step (4) gained, the PVC ball that a layer thickness is 3mm is spread above rich copper liquid, the particle diameter of PVC ball is 3mm, to absorb the irritant gas of releasing in electrolytic deposition process, cathode material adopts titanium plate, and anode material adopts lead-calcium-tin alloy plate, and control flume voltage is 3.2V, interpole gap is 10cm, and current density is 350A/m
2, temperature is 30 DEG C and carries out electrodeposition 5h, and in electrolytic deposition process, the copper segregation in rich copper liquid, on the surface of cathode material, finally obtains highly purified copper on cathode material, and its purity is 99.99% after testing, thus completes the extraction of metallic copper in old circuit board;
After above-mentioned electrodeposition, after copper segregation to the surface of cathode material in rich copper liquid, the poor copper liquid of gained can return to be applied as strip liquor, in order to carry out the copper of stripping in copper-loaded organic phase.
The above is only the citing of embodiments of the present invention; for those skilled in the art; under the prerequisite not departing from the technology of the present invention principle, can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (3)
1. from old circuit board, extract a method for metallic copper, it is characterized in that specifically comprising the following steps:
(1), the fragmentation of old circuit board
The old circuit board removing components and parts is broken into bulk, then pulverize with pulverizer, then 30 mesh sieves are crossed, the particle powder of gained, first selection by winnowing is carried out, metallic particles powder is separated with non-metallic particle powder, then the metallic particles powder of gained is carried out electric separation to remove the part iron in metallic particles powder, thus obtain the higher metal concentrate of copper content;
(2), the leaching of cupric ion
Sodium chlorate, the vitriol oil and water are carried out being hybridly prepared into the leaching agent aqueous solution, wherein density of sodium chlorate is 0.05 ~ 0.5mol/L, and sulfuric acid concentration is 0.1 ~ 5mol/L;
Join in reactor by the leaching agent aqueous solution, then add the metal concentrate that step (1) obtains, then controlling temperature of reaction kettle is 20-80 DEG C, and rotating speed is that 500r/min carries out Oxidation Leaching reaction 0.5-3.0h, obtains copper leach liquor after reaction terminates;
The add-on of above-mentioned metal concentrate, in metal concentrate: the leaching agent aqueous solution is that the ratio of 100g ︰ 2.5L calculates;
(3), solid-liquid separation
The copper leach liquor of step (2) gained is removed solid matter through centrifugation or Filter Press, obtains filtrate;
(4), cupric ion is purified
By the filtrate of step (3) gained through five grades extraction, secondary back extraction, obtain rich copper liquid;
Described five grades extraction, namely at normal temperatures, with organic extractant continuous extraction 5 times, is extracted into the selective copper in filtrate in organic extractant, obtains copper-loaded organic phase, and in each extraction process, organic extractant and leach liquor is in a ratio of 1 ︰ 4 ~ 4 ︰ 1;
Described organic extractant is that lix984, N910 or DZ973N and 26# kerosene calculate according to volume percent, and namely lix984, N910 or DZ973N:26# kerosene is that the ratio of 10 ~ 30%:70 ~ 90% mixes;
Described secondary back extraction, the copper-loaded organic phase strip liquor by gained after five grades extraction carries out continuous back extraction 2 times at normal temperatures, and in each stripping process, the volume ratio of copper-loaded organic phase and strip liquor is 1 ︰ 4 ~ 4 ︰ 1;
The aqueous sulfuric acid of described strip liquor to be concentration be 1 ~ 5mol/L;
(5), electrodeposition carries copper
The rich copper liquid of step (4) gained is put into electrodeposition pond, then on rich copper liquid, the PVC ball that a layer thickness is 2 ~ 5mm is spread, the particle diameter of PVC ball is 2 ~ 5mm, cathode material adopts titanium plate, stainless steel plate or fine copper plate, anode material adopts lead-calcium-tin alloy plate, the voltage controlling electrodeposition pond is 1.5 ~ 4.5V, and interpole gap is 2 ~ 16cm, and current density is 50 ~ 700A/m
2, temperature is 20 ~ 60 DEG C and carries out electrodeposition 0.5 ~ 10h, finally on cathode material, obtains highly purified copper, thus completes the extraction of metallic copper in old circuit board.
2. a kind of method extracting metallic copper from old circuit board as claimed in claim 1, it is characterized in that the bulk described in fragmentation of step (1) old circuit board, its weight is 3 kilograms.
3. a kind of method extracting metallic copper from old circuit board as claimed in claim 1, is characterized in that the reactor described in step (2) is titanium reactor or ceramic reactor.
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| CN113073200A (en) * | 2021-04-07 | 2021-07-06 | 广东明方科技有限公司 | Waste circuit board copper metal enrichment extraction device and extraction method thereof |
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