CN104328280B - Recovery method and the equipment of all-metal composition in a kind of discarded flex circuit application - Google Patents
Recovery method and the equipment of all-metal composition in a kind of discarded flex circuit application Download PDFInfo
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- CN104328280B CN104328280B CN201410542352.XA CN201410542352A CN104328280B CN 104328280 B CN104328280 B CN 104328280B CN 201410542352 A CN201410542352 A CN 201410542352A CN 104328280 B CN104328280 B CN 104328280B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to solid waste resource recovery and noble metal, non-ferrous metal recovery technology field, be specially recovery method and the equipment of all-metal composition in a kind of discarded flex circuit application. The present invention adopts cyclic aeration formula reactor, and the method combining with chemical method by microbial method realizes metal recovery. The inventive method produces without waste water and waste gas, realize recycling of solution, present device is cyclic aeration formula reactor, energy consumption is low, floor space is little, and reactor bottom aeration and leachate form stirring system while circulating, and discarded flex circuit application powder is fully contacted with solution, at the temperature of 25-30 DEG C, the metal ingredient that can realize efficient stable leaches.
Description
Technical field
The present invention relates to recovery method and the equipment of all-metal composition in a kind of discarded flex circuit application, belong to solid discardedThing resource and noble metal, non-ferrous metal recovery technology field.
Background technology
Flex circuit application is the printed circuit board of making as base material taking polyimides or polyester film, have high reliability andThe advantage of flexible, the application of flex circuit application makes electronic product (notebook, mobile phone) towards lightweight, miniaturization, thinType develops into reality. Due to obvious advantage and the potential ability of flex circuit application, it is on wiring board production & marketingStatus is more and more subject to people's understanding and attention, thereby the output value of flex circuit application is just with 20% average annual speed increment.
In actual application, in order to improve power-efficient, reduce High-frequency Interference, on flex circuit application, cover one deckCopper; Meanwhile, in order to extend the service life of flex circuit application, be covered with the gold of good stability at flex circuit application contact position.These factors make to contain in flex circuit application abundant gold, copper and nickel, in metals resources day by day deficient today, scratch from discardedProperty extract gold, copper, nickel in wiring board, there is very important value and significance.
Also do not have at present pertinent literature report how from flex circuit application, to extract metal, and for utilizing microbial methodExtract in the document of metal in rigidity wiring board, in the laboratory lab scale stage, the leaching device that researcher adopts is mostly shaking flaskLeach, the shortcoming of this mode is to carry out small-scale Leaching reaction; After further amplifying, the leaching device of employing is moreBe the reactor with agitating function only, the shortcoming of this mode is in the time adding more circuit board powder, simply stirsMix and can not make circuit board powder and nutrient solution fully mix, in addition, the shearing force that stirring produces also can be destroyed and have a liking for acid oxidase AsiaThe normal growth of iron Thiobacillus, thus the efficiency of metal is leached in impact.
After scale-up, in order further to improve the effect of having a liking for metal in the ferrous bioleaching flex circuit application of acid oxidaseRate, the present invention intends adopting leachate to circulate in reactor and pass into the technology that filtrated air combines in reactorPrepare leaching device.
Summary of the invention
In order to overcome the deficiencies in the prior art, object of the present invention aims to provide all-metal in a kind of discarded flex circuit applicationThe recovery method of composition and equipment, device therefor of the present invention, according to flex circuit application powder characteristics design after fragmentation, is established by thisStandby, can fully guarantee that particle is suspended in solution, avoid the particle structure fine and close because stack forms, really fungus preserving liquid can be fullyContact with particle. In the inventive method, leachate used can not produce harm to human body, and leachate recycles, without waste waterDischarge, can efficiently move, and improves the leaching rate of copper, nickel.
The present invention utilizes microbial method in cyclic aeration formula reactor, to leach copper, the nickel in discarded flex circuit application, andUtilize thiosulfate technique to extract and leach the gold in rear waste residue.
In the present invention, will discard flex circuit application powder and be placed in cyclic aeration formula reactor, and utilize microorganism leaching uselessAbandon copper, nickel in flex circuit application powder, copper, oxidized copper sulphate, the nickelous sulfate of being dissolved as of nickel, after filtration, the extraction of filtrate process-After reextraction-electrolysis process, obtain high-purity copper, nickel, the raffinate after extraction returns to leaching section again and recycles. UselessSlag adopts thiosulfate technique to reclaim gold wherein.
The recovery method of all-metal composition in a kind of discarded flex circuit application provided by the invention, it adopts cyclic aeration formulaReactor carries out metal recovery, and concrete steps are as follows:
(1) preparation 9K fluid nutrient medium, adjusts pH2.0 ~ 2.5 with sulfuric acid, then 9K fluid nutrient medium good acidifying is joinedIn cyclic aeration formula reactor;
(2), at 25-30 DEG C of temperature, have a liking for the ferrous Thiobacillus of acid oxidase by what cultivate through domestication(Acidithiobacillusferrooxidans) be inoculated in cyclic aeration formula reactor by inoculum concentration 5～15%;
(3) the discarded flex circuit application powder after fragmentation is joined in cyclic aeration formula reactor;
(4) ON cycle aeration reactor, at 25-30 DEG C of temperature, leach metallic copper in discarded flex circuit application,Nickel; After leaching completes, leachate is moved into liquid storage tank, filter, obtain filtrate and filter residue; Wherein: aerate flux is 0.5～1.5L/min, leachate circulation rate is 0.5～1.5L/min, leaching time is 5-7d;
(5) filtrate, through extraction-reextraction-electrolysis process, is realized the concentration and separation of metallic copper, nickel, obtains high-purityCopper, nickel;
(6) adopt thiosulfate technique to reclaim the gold in filter residue.
In the present invention, described 9K Liquid Culture based component is: FeSO4·7H2O、(NH4)2SO4、K2HPO4、KCl、MgSO4·7H2O、Ca(NO3)2And deionized water.
The present invention also provides a kind of equipment adopting in all-metal composition process in discarded flex circuit application that reclaims, and it is for followingRing aeration reactor, comprises reactor body, aeration opening, air compressor, circulation conduit and drawing liquid pump; Described reactorThe bottom upper horizontal of main body arranges several aeration opening, and air compressor is aseptic to passing in reactor body by aeration openingAir, the two ends of described drawing liquid pump are connected with circulation conduit respectively, and the leachate in reactor body is circulated.
Beneficial effect of the present invention is:
(1) the present invention adopts the technology that microbial method combines with chemical method to realize all-metal one-tenth in discarded flex circuit applicationThe recovery dividing, and obtain highly purified copper, nickel and gold.
(2) in the present invention, filtrate is squeezed into mixer-settler by pump and is carried out extracting-back extraction and get, and through extraction, (extractant isRE609) after, the organic phase of supported copper, nickel enters into back extraction workshop section, and rich copper, nickel solution that back extraction obtains enter into electrolytic cell. ObtainObtain high-purity copper, nickel. Wherein, raffinate enters raffinate storage pool, turns back in reactor after scraping off oil slick, and poor copper, nickel haveThe extraction section that machine turns back to mixer-settler mutually recycles, and after poor copper, the nickel electrolyte that electrolysis obtains added sulfuric acid, can be used asBack washing agent Returning utilization. Recycling of raffinate, poor copper, nickel organic phase and poor copper, nickel electrolyte, has realized the present invention without uselessThe target of water discharge, is safe from harm to environment and human body.
(3) the present invention adopts cyclic aeration formula reactor energy consumption low, and floor space is little, by reactor bottom aeration andLeachate circulates, and can fully guarantee that particle is suspended in solution, avoids the particle structure fine and close because stack forms, reallyFungus preserving liquid can fully contact with particle. Under the cryogenic temperature of 25-30 DEG C, get final product the leaching all-metal composition of stability and high efficiency.
Brief description of the drawings
Fig. 1 is the technological process that the present invention reclaims all-metal composition in discarded flex circuit application powder.
Fig. 2 is that the present invention reclaims all-metal composition cyclic aeration formula structure of reactor used in discarded flex circuit application and showsIntention.
Number in the figure: 1-reactor body; 2-aeration opening; 3-air compressor; 4-circulation conduit; 5-drawing liquid pump.
Detailed description of the invention
Be illustrated in figure 1 the technological process that the present invention reclaims all-metal composition in discarded flex circuit application powder. Now combinationAccompanying drawing is described as follows to technological process:
(1) first prepare 9K fluid nutrient medium and join in reactor, with sulfuric acid tune initial pH to 2.0 ~ 2.5 of leachate;Wherein FeSO4·7H2O is 40g/L, (NH4)2SO4For 3g/L, K2HPO4For 0.5g/L, KCl are 0.1g/L, MgSO4·7H2O is0.5g/L、Ca(NO3)2For 0.01g/L, deionized water;
(2), at 25-30 DEG C, have a liking for the ferrous Thiobacillus (Acidithiobacillus of acid oxidase by what cultivate through domesticationFerrooxidans) be inoculated in reactor by inoculum concentration 10%;
(3) the discarded flex circuit application powder after fragmentation is put in cyclic aeration formula reactor;
(4) ON cycle aeration reactor, at 25-30 DEG C of temperature, leach metallic copper in discarded flex circuit application,Nickel; After leaching completes, leachate is moved into liquid storage tank, filter, obtain filtrate and filter residue; Wherein: aerate flux 0.5～1.5L/Min, leachate circulation rate 0.5～1.5L/min, leaching time is 5-7d;
(5) after leaching process completes, adopt self priming pump that leachate is moved into liquid storage tank, filter;
(6) filtrate is squeezed into mixer-settler by pump and is carried out extractive reaction, and extractant is RE609, and supported copper, nickel has afterwardsMachine enters into back extraction workshop section mutually, and raffinate enters raffinate storage pool, scrapes off after oil slick and turns back in leaching tanks and recycle;
(7) organic phase of supported copper, nickel is after back extraction, and the rich copper, the nickel solution that obtain enter into electrolytic cell, poor copper, nickelThe extraction section that organic phase turns back to mixer-settler recycles;
(8) at current density 100-150A/m2, voltage is 1-1.5V, positive plate, minus plate are all corrosion resistant plate situationUnder, rich copper, nickel solution are carried out to electrolysis, obtain high-purity copper, nickel;
(9) adopt thiosulfate technique to reclaim the gold in filter residue.
Be illustrated in figure 2 the present invention and reclaim all-metal composition cyclic aeration formula reaction used in discarded flex circuit applicationDevice, now by reference to the accompanying drawings present device is described as follows:
Cyclic aeration formula reactor apparatus of the present invention mainly comprises: reactor body 1, is and has a liking for the ferrous Thiobacillus of acid oxidaseWith discarded flex circuit application reacting environment, it also comprises aeration opening 2, air compressor 3 and circulation conduit 4 and drawing liquid pump 5. Pass throughAir compressor 3 passes into filtrated air in reactor body 1, and the downward design of aeration opening 2 can be avoided discarded flex circuit applicationPowder is blocked aeration opening; In addition, also through circulating pump 4, nutrient solution (leachate) can be circulated by drawing liquid pump 5, withThe modular design of upper two kinds of modes makes to have a liking for the ferrous Thiobacillus of acid oxidase can fully mix with discarded flex circuit application powder, strengthensLeaching rate.
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1
Preparation 9K fluid nutrient medium, its component content: FeSO4·7H2O is 40g/L, (NH4)2SO4For 3g/L, K2HPO4For0.5g/L, KCl are 0.1g/L, MgSO4·7H2O is 0.5g/L, Ca (NO3)2For 0.01g/L, all the other are deionized water. To tameThe ferrous Thiobacillus of acid oxidase (Acidithiobacillusferrooxidans) of having a liking for crossing is inoculated into reactor by inoculum concentration 10%In, form leaching liquid with culture medium, the discarded flex circuit application powder of input and the ratio of leaching liquid, solid-to-liquid ratio is 1: 40.Adjusting the initial pH of leaching liquid with sulfuric acid is 2.5, and aerate flux 1L/min, leachate circulation rate 1L/min leach 5d at 28 DEG C.The copper leaching rate calculating after testing in leachate is 90.1%, and nickel leaching rate is 85.9%, utilizes thiosulfate technique from leachingFilter residue in to put forward golden efficiency be 92.3%.
Embodiment 2
Preparation 9K fluid nutrient medium, its component content: FeSO4·7H2O is 40g/L, (NH4)2SO4For 3g/L, K2HPO4For0.5g/L, KCl are 0.1g/L, MgSO4·7H2O is 0.5g/L, Ca (NO3)2For 0.01g/L, all the other are deionized water. To tameThe ferrous Thiobacillus of acid oxidase (Acidithiobacillusferrooxidans) of having a liking for crossing is inoculated into reactor by inoculum concentration 10%In, form leaching liquid with culture medium, the discarded flex circuit application powder of input and the ratio of leaching liquid, solid-to-liquid ratio is 1: 20.Adjusting the initial pH of leaching liquid with sulfuric acid is 2.5, and aerate flux 1L/min, leachate circulation rate 1L/min leach 6d at 30 DEG C.Calculating after testing copper leaching rate in leachate is 88.6%, and nickel leaching rate is 83.5%, utilize thiosulfate technique from leachIn filter residue, putting forward golden efficiency is 91.4%.
Embodiment 3
Preparation 9K fluid nutrient medium, its component content: FeSO4·7H2O is 40g/L, (NH4)2SO4For 3g/L, K2HPO4For0.5g/L, KCl are 0.1g/L, MgSO4·7H2O is 0.5g/L, Ca (NO3)2For 0.01g/L, all the other are deionized water. To tameThe ferrous Thiobacillus of acid oxidase (Acidithiobacillusferrooxidans) of having a liking for crossing is inoculated into reactor by inoculum concentration 10%In, form leaching liquid with culture medium, the discarded flex circuit application powder of input and the ratio of leaching liquid, solid-to-liquid ratio is 1: 10.Adjusting the initial pH of leaching liquid with sulfuric acid is 2.0, and aerate flux 1L/min, leachate circulation rate 1L/min leach 7d at 28 DEG C.Calculating after testing copper leaching rate in leachate is 86.2%, and nickel leaching rate is 84.1%, utilize thiosulfate technique from leachIn filter residue, putting forward golden efficiency is 89.8%.
Claims (2)
1. a recovery method for all-metal composition in discarded flex circuit application, is characterized in that, it adopts cyclic aeration formula anti-Answer device to carry out metal recovery, described cyclic aeration formula reactor, comprises reactor body, aeration opening, and air compressor, circulation is ledPipe and drawing liquid pump; The bottom upper horizontal of described reactor body arranges several aeration opening, and described air compressor is by exposing to the sunGas port passes into filtrated air in reactor body, and the two ends of described drawing liquid pump are connected with circulation conduit respectively, make reactorLeachate in main body circulates; Concrete steps are as follows:
(1) preparation 9K fluid nutrient medium, adjusts pH2.0 ~ 2.5 with sulfuric acid, then 9K fluid nutrient medium good acidifying is joined to circulationIn aeration reactor;
(2), at 25-30 DEG C of temperature, have a liking for the ferrous Thiobacillus (Acidithiobacillus of acid oxidase by what cultivate through domesticationFerrooxidans) be inoculated in cyclic aeration formula reactor by inoculum concentration 5～15%;
(3) the discarded flex circuit application powder after fragmentation is joined in cyclic aeration formula reactor;
(4) ON cycle aeration reactor, at 25-30 DEG C of temperature, leaches metallic copper, nickel in discarded flex circuit application; SoakAfter having gone out, leachate is moved into liquid storage tank, filter, obtain filtrate and filter residue; Wherein: aerate flux is 0.5～1.5L/min,Leachate circulation rate is 0.5～1.5L/min, and leaching time is 5-7d;
(5) filtrate, through extraction-reextraction-electrolysis process, is realized the concentration and separation of metallic copper, nickel, acquisition high-purity copper,Nickel;
(6) adopt thiosulfate technique to reclaim the gold in filter residue.
2. recovery method according to claim 1, is characterized in that: in step (1), and described 9K Liquid Culture based componentFor: FeSO4·7H2O、(NH4)2SO4、K2HPO4、KCl、MgSO4·7H2O、Ca(NO3)2And deionized water.
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| CN108004402B (en) * | 2015-05-13 | 2019-03-19 | 江苏理工学院 | Method for leaching copper in waste printed circuit board by using thiobacillus ferrooxidans |
| CN105296760A (en) * | 2015-11-19 | 2016-02-03 | 四川长虹电器股份有限公司 | Metal recycling reaction device and metal recycling method thereof |
| ES2707353B2 (en) * | 2018-04-25 | 2019-11-26 | Univ Catalunya Politecnica | METHOD FOR BIOLOGICAL RECOVERY OF METALS IN ELECTRICAL AND ELECTRONIC WASTE |
| WO2022162252A1 (en) | 2021-01-28 | 2022-08-04 | Universitat Politecnica De Catalunya | Method for biological recovery of metals from electrical and electronic waste |
| CN113355519B (en) * | 2021-06-03 | 2022-11-22 | 上海第二工业大学 | Method for leaching copper in waste circuit board by using microwave-enhanced thiobacillus ferrooxidans |
| CN115505749A (en) * | 2022-11-04 | 2022-12-23 | 北京工业大学 | Thiosulfate gold leaching solution and method for leaching gold in waste circuit board |
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| CN100404705C (en) * | 2006-04-24 | 2008-07-23 | 南京大学 | Method for extracting metal copper using microbe and its use |
| CN101538651A (en) * | 2009-04-22 | 2009-09-23 | 上海第二工业大学 | Method for recycling metal |
| CN101760619A (en) * | 2009-12-31 | 2010-06-30 | 惠州市雄越保环科技有限公司 | Method for recovering metallic copper in mud by using microorganism and special device |
| CN102912126B (en) * | 2012-11-08 | 2014-06-11 | 常州纺织服装职业技术学院 | Rotary-type bioreactor |
| CN203033993U (en) * | 2012-11-28 | 2013-07-03 | 上海第二工业大学 | Fermentation device for acidophilic bacterium culture |
| CN104073639B (en) * | 2014-06-24 | 2016-04-20 | 上海第二工业大学 | A kind of two-step approach reclaims the method for copper and gold from waste electronic material |
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