CN103320619B - Method and device for biological leaching of precious metals from metal mixed particles of crushed waste circuit boards - Google Patents
Method and device for biological leaching of precious metals from metal mixed particles of crushed waste circuit boards Download PDFInfo
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- CN103320619B CN103320619B CN201310262162.8A CN201310262162A CN103320619B CN 103320619 B CN103320619 B CN 103320619B CN 201310262162 A CN201310262162 A CN 201310262162A CN 103320619 B CN103320619 B CN 103320619B
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- 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 relates to a method and a device for biological leaching of precious metals from metal mixed particles of crushed waste circuit boards. The method comprises the following steps of: firstly inoculating pseudomonas into a thallus culture device, culturing for about 24h, then sending into a microbial leaching reactor, simultaneously adding the metal mixed particles of the crushed waste circuit boards into the reactor, and sequentially dissolving general metals and the precious metals in the metal mixed particles with hydrocyanic acid secreted by the pseudomonas; firstly filtering a mixed solution of general metal ions which are dissolved out and thalli of the pseudomonas through a compact filter bed, and enabling a filtrate to flow into a metal ion collection device; closing the microbial leaching reactor once a metal ion online monitoring system monitors the existence of second metal ions in the metal ion collection device, wherein the extraction of one metal ion solution is ended at this time; repeating the leaching extraction process to sequentially get the general metals with higher purity and a precious metal single ion solution; and recovering the metal ions in the solution through a metal replacement method. The method and the device, disclosed by the invention, have the characteristics of low cost, high efficiency, no pollution and the like.
Description
Technical field
The present invention relates to separation and the recovery of waste printed circuit board precious metal, is a kind of technological method and device of waste printed circuit board high added value resource utilization.
Background technology
Along with science and technology constantly progress, the appearance of electric equipment products makes the standard of living of people day by day improve.Circuit card is as the core component of various electric equipment products, and its learies constantly becomes large along with the increase of waste and old electric electrical equipment amount.Containing abundant metals resources in waste printed circuit board, comprise the precious metal such as gold and silver, palladium, the non-ferrous metals such as copper, aluminium, zinc, tin, lead, the base metals such as iron.In addition, the nonmetal resource that content is a large amount of is gone back in waste printed circuit board.Therefore, the resource utilization of waste printed circuit board has become the hot issue in resource recovery field.At present, about the patented technology application of discarded circuit board resource utilization mainly concentrates on metal and nonmetal resource reclaim two aspects.Metals resources reclaims the method adopted and mostly is Physical (" fragmentation of waste and old printed circuit board and high-pressure electrostatic separation method ", the patent No. 200510023785.5, " high-pressure electrostatic separation method of waste PCB grains and device ", the patent No. 200510023788.9) and Chemical Leaching method (method of tin, copper and lead " in a kind of Selectively leaching discarded circuit board ", application number 200910082443.9).In physical recovering method waste printed circuit board during the metals resources such as copper, zinc, lead, usually adopt the method that fragmentation-physical separation combines.This method successfully can reclaim the metalliferous material of more than 95% from smashing waste circuit card.But; the deficiency that Physical shows when separating metal granular mixture in ability (embodies separation rate according to adopted method difference not high; or cost of equipment is too high; the situation that production cost is too high); especially (bullion content is less to be embodied in recovery precious metal aspect; and the more difficult separation of general physical separation method, or high cost).When Chemical Leaching method reclaims the metals resources in waste printed circuit board, the rate of recovery is high, and can reclaim most of metal.But Chemical Leaching method can bring serious secondary pollution, as waste water, spent acid mist etc., bring heavy environmental protection pressure to whole production technique.Meanwhile, the use of a large amount of chemical brings potential safety hazard to production process, and the recovery of precious metal may also need to use chloroazotic acid, the huge cytotoxic chemical articles for use such as prussic acid.
Bioleaching is a kind of a kind of method utilizing the meta-bolites given off in microorganism growth, metabolic process to dissolve, leach target substance, has the advantage of environmental protection, low cost.The precious metal in Microorganism Leaching waste printed circuit board is utilized to be feasible in theory.Unique unfortunately the usual efficiency of bioleaching process is lower, and especially when processing waste printed circuit board, its nonmetallic ingredient and other metal component can destroy the leaching process of precious metal, reduces the leaching rate of precious metal.
Therefore, improving metal leaching rate is that can microbe leaching-out method apply the problem needing solution badly in waste printed circuit board precious metal removal process.About the negative impact of waste circuit board non-metal component to precious metal Bioleaching speed can be removed by physical partition method.The current patent application about the recovery of waste printed circuit board precious metal and pertinent literature are reported less, and the relevant information being reclaimed precious metal in waste printed circuit board by efficient Bioleaching technology and device is almost had no.
Summary of the invention
The object of this invention is to provide a kind of smashing waste board metal composite grain precious metal bioleaching process and device, the high added value that the present invention not only achieves waste printed circuit board reclaims, and also has efficient and eco-friendly feature.
The object of the invention is to be achieved through the following technical solutions, smashing waste board metal composite grain precious metal bioleaching process, comprises the following steps:
Smashing waste board metal composite grain precious metal bioleaching process, is characterized in that, comprise the following steps:
1. pseudomonas is cultivated, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached and produces the strongest state of prussic acid ability, the metal mixed particle that the pseudomonas and smashing waste circuit card that reach the strongest state of product prussic acid ability obtain after high-voltage electrostatic sorting is at room temperature reacted, pseudomonas secretes prussic acid, metal mixed particle carries out metal Leaching reaction under prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, is secondly inertia precious metal;
2. the metal ion solution of leaching is obtained metal ion solution through fine and close depth filtration, deep bed filtration, collect filtering the metal ion solution obtained, there are two metal ion species once monitor in the metal ion solution collected, stop the collection of metal ion solution at once, to ensure the purity of the metal ion solution collected; Repeat to leach leaching process, obtain the single ionic solution of common metal, the single ionic solution of precious metal successively;
3. the metal single ionic solution that step (2) obtains is displaced common metal and precious metal respectively by the mode of metal replacement.
Realize the device of above-mentioned smashing waste board metal composite grain precious metal bioleaching process, comprise yeast culture device, Microorganism Leaching reactor, metal ion collector, metal ion online monitoring system and transferpump, yeast culture device connects Microorganism Leaching reactor by transferpump, metal ion collector connection metal ion online monitoring system; Yeast culture device is provided with bacterization entrance; Microorganism Leaching reactor is provided with metal mixed particle input aperture, Microorganism Leaching reactor lower part is provided with fine and close filter bed, the void size of fine and close filter bed is less than pseudomonad cells size, slide plate is provided with bottom fine and close filter bed, described slide plate comprises two sheet materials, one of them sheet material is processed hollow slideway, another sheet material one end to be arranged in hollow slideway and to move around in hollow slideway; The Microorganism Leaching reactor bottom corresponding with slide plate arranges transferpump, and Microorganism Leaching reactor is by transferpump connection metal ion collector.
Preferably, agitator is provided with in described Microorganism Leaching reactor.
Preferably, described metal ion collector is provided with metal ion solution outlet.
Compared with prior art, the present invention has following beneficial effect:
The first, the thalline of inoculation is pseudomonas, has the ability of secretion prussic acid, has the ability of decomposing prussic acid under the condition of nutritive substance shortage simultaneously; Prussic acid preferentially leaches active metal, is secondly inertia precious metal; After Leaching reaction terminates, pseudomonas can decompose remaining prussic acid, avoids secondary pollution.
The second, the void size of fine and close filter bed is less than pseudomonad cells size, while ensureing that metal ion solution can leach smoothly, pseudomonad cells is stayed in Bioleaching reactor.
3rd, slide plate is can the dividing plate that pulls of both sides, and metal ion solution can be made after opening to flow out Microorganism Leaching reactor smoothly.
4th, metal ion on-line monitoring system in metal ion solution collector once monitor the second metal ion should close slide plate immediately, ensure the purity of metal ion solution in metal ion solution collector, the negative impact of metal component to precious metal Bioleaching speed can be eliminated.
5th, the common metal ion be first dissolved out and pseudomonas thalline mixed solution, through the filtration of fine and close filter bed, enter in metal ion collector at the flows by action of transferpump; Equip metal ion on-line monitoring system in metal ion collector, once monitor out the second metal ion, close slide plate, now a kind of metal ion solution extracts and terminates; Metal ion solution in metal ion collector is exported, obtains the single metal ion solution that purity is higher; Repeat slide plate to open and the leaching leaching process of closing, the higher common metal of purity and precious metal single ionic solution can be obtained successively; Metal ion in solution can be reclaimed by the method for metal replacement.Compare with physical recovering method smashing waste circuit card precious metal with chemical method, the present invention has the features such as cost is low, efficient, pollution-free, overcomes domestic employing Physical and is difficult to reclaim the shortcoming that waste printed circuit board precious metal and chemical method can produce serious secondary pollution.
Accompanying drawing explanation
Fig. 1 realizes smashing waste board metal composite grain precious metal Bioleaching apparatus structure schematic diagram of the present invention;
In figure: 1 is bacterization entrance; 2 is yeast culture device; 3 is transferpump; 4 is Microorganism Leaching reactor; 5 is metal mixed particle input aperture; 6 is agitator; 7 is fine and close filter bed; 8 is slide plate; 9 is metal ion solution collector; 10 is metal ion online monitoring system; 11 is metal ion solution outlet.
Embodiment
Embodiment below in conjunction with example is further explained the present invention.
Embodiment 1
Smashing waste board metal composite grain precious metal bioleaching process, is characterized in that, comprise the following steps:
1. pseudomonas is cultivated, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached and produces the strongest state of prussic acid ability, the metal mixed particle that the pseudomonas and smashing waste circuit card that reach the strongest state of product prussic acid ability obtain after high-voltage electrostatic sorting is at room temperature reacted, pseudomonas secretes prussic acid, metal mixed particle carries out metal Leaching reaction under prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, is secondly inertia precious metal;
2. the metal ion solution of leaching is obtained metal ion solution through fine and close depth filtration, deep bed filtration, collect filtering the metal ion solution obtained, there are two metal ion species once monitor in the metal ion solution collected, stop the collection of metal ion solution at once, to ensure the purity of the metal ion solution collected; Repeat to leach leaching process, obtain the single ionic solution of common metal, the single ionic solution of precious metal successively;
3. the metal single ionic solution that step (2) obtains is displaced common metal and precious metal respectively by the mode of metal replacement.
A device for above-mentioned smashing waste board metal composite grain precious metal bioleaching process, comprises yeast culture device 2, Microorganism Leaching reactor 4, metal ion solution collector 9, metal ion online monitoring system 10 and transferpump 3.
Yeast culture device 2 connects Microorganism Leaching reactor 4 by transferpump 3.Metal ion solution collector 9 connection metal ion online monitoring system 10.
Yeast culture device 2 is provided with bacterization entrance 1.
Microorganism Leaching reactor 4 is provided with metal mixed particle input aperture 5.Microorganism Leaching reactor 4 bottom is provided with fine and close filter bed 7.The void size of fine and close filter bed 7 is less than pseudomonad cells size, is provided with slide plate 8 bottom fine and close filter bed 7.Slide plate 8 comprises two sheet materials, one of them sheet material is processed hollow slideway, and another sheet material one end to be arranged in hollow slideway and to move around in hollow slideway.Skateboard is two panels slide plate, is thinner entity hard slide plate, and the other side is thicker hollow hard slide plate, and when slide plate needs to open, thinner slide plate can receive in the chamber of thicker hollow slide plate, opens with side bottom ensureing Leaching reaction device.
The Microorganism Leaching reactor bottom corresponding with slide plate 8 arranges transferpump 3, and Microorganism Leaching reactor 4 is by transferpump 3 connection metal solion collector 9.Transferpump delivery spout is connected on the Leaching reaction wall below slide plate, to ensure that under the condition that slide plate is opened, the metal ion solution of outflow enters transferpump delivery spout, is transported in metal ion collector after solid filter bed filters.
Agitator 6 is provided with in Microorganism Leaching reactor 4.
Metal ion solution collector 9 is provided with metal ion solution outlet 11.
Embodiment 2
First be inoculated in yeast culture device 2 by pseudomonas by bacterization entrance 1, the substratum in yeast culture device 2 is beef extract-peptone-sodium-chlor substratum; Cultivate for some time in yeast culture device 2 after, pseudomonas is had and produces prussic acid ability (cultivating about 24 hours) the most by force, by transferpump 3, pseudomonas solution pump is entered in Microorganism Leaching reactor 4.
Meanwhile, by metal mixed particle input aperture 5, smashing waste board metal composite grain is joined in Microorganism Leaching reactor 4; In Microorganism Leaching reactor 4, pseudomonas secretes prussic acid dissolves the common metal in metal mixed particle, precious metal successively, makes them become ionic state and enters in solution.Under the condition that slide plate 8 side is opened, the common metal ion be first dissolved out and pseudomonas thalline mixed solution, through the filtration of fine and close filter bed 7, go out Microorganism Leaching reactor 4 at the flows by action of transferpump 3, flow in metal ion solution collector 9.
Equip metal ion on-line monitoring system 10 in metal ion solution collector 9, once monitor out the second metal ion, should close slide plate 8 immediately, now a kind of metal ion solution extracts and terminates; Metal ion solution in metal ion solution collector 9 is exported through delivery port 11, thus obtains the higher single metal ion solution of purity; Repeat slide plate 8 to open and the leaching leaching process of closing, the higher common metal of purity and precious metal single ionic solution can be obtained successively.Metal ion in solution can be reclaimed by the method for metal replacement.
The method and device can obtain the single ionic solution of various metal in smashing waste circuit card, the various common metal of separation and Extraction and precious metal.
The thalline of inoculation is pseudomonas, has the ability of secretion prussic acid, has the ability of decomposing prussic acid under the condition of nutritive substance shortage simultaneously; Prussic acid preferentially leaches active metal, is secondly inertia precious metal; After Leaching reaction terminates, pseudomonas can decompose remaining prussic acid, avoids secondary pollution.
The void size of fine and close filter bed is less than pseudomonad cells size, while ensureing that metal ion solution can leach smoothly, pseudomonad cells is stayed in Bioleaching reactor;
Slide plate is can the dividing plate that pulls of both sides, and metal ion solution can be made after opening to flow out Microorganism Leaching reactor smoothly;
Metal ion on-line monitoring system in metal ion solution collector once monitor the second metal ion should close slide plate immediately, ensure the purity of metal ion solution in metal ion solution collector, the negative impact of metal component to precious metal Bioleaching speed can be eliminated.
First the common metal ion be dissolved out and pseudomonas thalline mixed solution, through the filtration of fine and close filter bed, enter in metal ion collector at the flows by action of transferpump; Equip metal ion on-line monitoring system in metal ion collector, once monitor out the second metal ion, close slide plate, now a kind of metal ion solution extracts and terminates; Metal ion solution in metal ion collector is exported, obtains the single metal ion solution that purity is higher; Repeat slide plate to open and the leaching leaching process of closing, the higher common metal of purity and precious metal single ionic solution can be obtained successively; Metal ion in solution can be reclaimed by the method for metal replacement.
Claims (4)
1. smashing waste board metal composite grain precious metal bioleaching process, is characterized in that, comprise the following steps:
1. pseudomonas is cultivated, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached and produces the strongest state of prussic acid ability, the metal mixed particle that the pseudomonas and smashing waste circuit card that reach the strongest state of product prussic acid ability obtain after high-voltage electrostatic sorting is at room temperature reacted, pseudomonas secretes prussic acid, metal mixed particle carries out metal Leaching reaction under prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, is secondly inertia precious metal;
2. the metal ion solution of leaching is obtained metal ion solution through fine and close depth filtration, deep bed filtration, the void size of fine and close filter bed is less than pseudomonad cells size; Collected by metal ion solution collector filtering the metal ion solution obtained, monitor in the metal ion solution collected once the metal ion on-line monitoring system in metal ion solution collector and there are two metal ion species, stop the collection of metal ion solution at once, to ensure the purity of the metal ion solution collected; Repeat to leach leaching process, obtain the single ionic solution of common metal, the single ionic solution of precious metal successively;
3. the metal single ionic solution that step (2) obtains is displaced common metal and precious metal respectively by the mode of metal replacement.
2. one kind realizes the device of smashing waste board metal composite grain precious metal bioleaching process according to claim 1, it is characterized in that, described device comprises yeast culture device, Microorganism Leaching reactor, metal ion solution collector, metal ion online monitoring system and transferpump, yeast culture device connects Microorganism Leaching reactor by transferpump, metal ion solution collector connection metal ion online monitoring system; Yeast culture device is provided with bacterization entrance; Microorganism Leaching reactor is provided with metal mixed particle input aperture, Microorganism Leaching reactor lower part is provided with fine and close filter bed, the void size of fine and close filter bed is less than pseudomonad cells size, slide plate is provided with bottom fine and close filter bed, described slide plate comprises two sheet materials, one of them sheet material is processed hollow slideway, another sheet material one end to be arranged in hollow slideway and to move around in hollow slideway; The Microorganism Leaching reactor bottom corresponding with slide plate arranges transferpump, and Microorganism Leaching reactor is by transferpump connection metal solion collector.
3. the device realizing smashing waste board metal composite grain precious metal bioleaching process according to claim 2, is characterized in that, be provided with agitator in described Microorganism Leaching reactor.
4. the device realizing smashing waste board metal composite grain precious metal bioleaching process according to claim 2, is characterized in that, described metal ion solution collector is provided with metal ion solution outlet.
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| CN201310262162.8A CN103320619B (en) | 2013-06-27 | 2013-06-27 | Method and device for biological leaching of precious metals from metal mixed particles of crushed waste circuit boards |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104726714B (en) * | 2013-09-30 | 2017-06-16 | 江苏理工学院 | A kind of method of copper in Mixed Microbes leaching discarded printed circuit boards |
| CN106011484B (en) * | 2016-07-08 | 2018-09-14 | 扬州大学 | A kind of waste printed circuit board precious metal recovery device based on production cyanogen biofilm reactor |
| CN107119194B (en) * | 2017-03-22 | 2018-11-20 | 中山大学 | A kind of the high-performance bio leaching method and device of waste and old circuit board noble metal |
| EP3415647A1 (en) * | 2017-06-13 | 2018-12-19 | B.R.A.I.N. Ag | A process for recovering precious metals from secondary resources |
| CN107746959B (en) * | 2017-11-17 | 2019-01-11 | 中山大学 | A kind of two step bioleaching process and device of total head recycling valuable metals in waste circuit board |
| CN113652351A (en) * | 2021-07-28 | 2021-11-16 | 中山大学 | Method and device for strengthening cyanogen production capacity of composite microorganism by external electric field |
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| CN1786222A (en) * | 2004-12-08 | 2006-06-14 | 浙江丰利粉碎设备有限公司 | Grinding recovery treatment technology of waste electron wiring board and its equipment |
| CN101538651A (en) * | 2009-04-22 | 2009-09-23 | 上海第二工业大学 | Method for recycling metal |
| CN102091711A (en) * | 2010-12-14 | 2011-06-15 | 惠州市雄越保环科技有限公司 | Device for recycling waste printed circuit board |
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| JP2007308762A (en) * | 2006-05-18 | 2007-11-29 | Osaka Univ | Low environmental load type metal recovery method using cyanogen formation and decomposition bacteria |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1786222A (en) * | 2004-12-08 | 2006-06-14 | 浙江丰利粉碎设备有限公司 | Grinding recovery treatment technology of waste electron wiring board and its equipment |
| CN101538651A (en) * | 2009-04-22 | 2009-09-23 | 上海第二工业大学 | Method for recycling metal |
| CN102091711A (en) * | 2010-12-14 | 2011-06-15 | 惠州市雄越保环科技有限公司 | Device for recycling waste printed circuit board |
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