CN103320619A - 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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- CN103320619A CN103320619A CN2013102621628A CN201310262162A CN103320619A CN 103320619 A CN103320619 A CN 103320619A CN 2013102621628 A CN2013102621628 A CN 2013102621628A CN 201310262162 A CN201310262162 A CN 201310262162A CN 103320619 A CN103320619 A CN 103320619A
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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
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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 is constantly progressive, the appearance of electric equipment products makes people's standard of living improve day by day.Circuit card is as the core component of various electric equipment productss, and its learies is along with the increase of waste and old electric electrical equipment amount constantly becomes big.Waste printed circuit board contains abundant metals resources, comprises precious metals such as gold and silver, palladium, non-ferrous metals such as copper, aluminium, zinc, tin, lead, base metals such as iron.In addition, go back a large amount of nonmetal resource of content in the waste printed circuit board.Therefore, the resource utilization of waste printed circuit board has become the hot issue in resource recovery field.At present, the patented technology application about the discarded circuit board resource utilization mainly concentrates on metal and two aspects of nonmetal resource recovery.Metals resources reclaims the method that adopts and mostly is physics method (" 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 and old printed circuit board particle and device ", the patent No. 200510023788.9) and chemical lixiviation process (" a kind of selectivity leaches tin in the discarded circuit board, copper and plumbous method ", application number 200910082443.9).When the physics method reclaims in the waste printed circuit board metals resources such as copper, zinc, lead, the method that adopts fragmentation-physical separation to combine usually.This method can success from the smashing waste circuit card, reclaim metalliferous material more than 95%.Yet; the physics method has shown the deficiency on the ability when the separating metal granular mixture (it is not high to embody separation rate according to the method difference that adopts; 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 general physical separation method is difficult the separation, or cost is too high).When the chemistry lixiviation process reclaims metals resources in the waste printed circuit board, rate of recovery height, and can reclaim most of metal.Yet chemical lixiviation process can bring serious secondary pollution, and as waste water, spent acid mist etc. have brought heavy environmental protection pressure for whole production technology.Simultaneously, the use of a large amount of chemical has brought potential safety hazard to production process, and the recovery of precious metal may also need to use chloroazotic acid, huge cytotoxic chemical articles for use such as prussic acid.
The biological leaching is a kind of meta-bolites dissolving that gives off in microorganism growth, the metabolic process, a kind of method that leaches target substance utilized, and has environmental protection, advantage cheaply.The precious metal that utilizes microorganism to leach in the waste printed circuit board is fully feasible in theory.Unique deficiency be that the common efficient of bioleaching process is lower, especially when handling waste printed circuit board, its nonmetallic ingredient and other metal component can destroy the leaching process of precious metal, reduce the leaching rate of precious metal.
Therefore, improving the metal leaching rate is that can microbe leaching-out method apply the problem of needing solution badly in waste printed circuit board precious metal removal process.Relevant waste circuit board non-metal component can be removed by physical partition method the negative impact of the biological leaching rate of precious metal.At present the patent application and the pertinent literature report that reclaim of relevant waste printed circuit board precious metal is less, reclaims the relevant information of precious metal in the waste printed circuit board by biological leaching-out technique and device efficiently and does not almost see.
Summary of the invention
The purpose of this invention is to provide a kind of smashing waste circuit card metal mixed particle precious metal bioleaching process and device, the present invention has realized that not only the high added value of waste printed circuit board reclaims, and also has efficient and eco-friendly characteristics.
The objective of the invention is to be achieved through the following technical solutions, smashing waste circuit card metal mixed particle precious metal bioleaching process may further comprise the steps:
Smashing waste circuit card metal mixed particle precious metal bioleaching process is characterized in that, may further comprise the steps:
1. cultivate pseudomonas, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached produce the strongest state of prussic acid ability, to reach and produce the prussic acid ability the pseudomonas of strong state and the metal mixed particle that the smashing waste circuit card obtains after the high pressure static electricity sorting at room temperature react, pseudomonas secretes prussic acid, the metal mixed particle carries out metal and leaches reaction under the prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, secondly is the inertia precious metal;
2. the metal ion solution that leaches is obtained metal ion solution through fine and close depth filtration, deep bed filtration, the metal ion solution that filtration obtains is collected, in case monitor when having two metal ion species in the metal ion solution of collecting, stop the collection of metal ion solution at once, with the purity of the metal ion solution that guarantees to collect; 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) is obtained displaces common metal and precious metal respectively by the mode of metal replacement.
Realize the device of above-mentioned smashing waste circuit card metal mixed particle precious metal bioleaching process, comprise yeast culture device, microorganism leaching reactor, metal ion collector, metal ion online monitoring system and transferpump, the yeast culture device connects microorganism by transferpump and leaches reactor, and the metal ion collector connects the metal ion online monitoring system; The yeast culture device is provided with the bacterization entrance; Microorganism is leached reactor and is provided with metal mixed particle input aperture, microorganism is leached reactor lower part and is provided with fine and close filter bed, the void size of fine and close filter bed is less than the pseudomonad cells size, fine and close filter bed bottom is provided with slide plate, described slide plate comprises two sheet materials, processing hollow slideway on one of them sheet material, another sheet material one end is arranged in the hollow slideway and in the hollow slideway and moves around; The microorganism corresponding with slide plate leached reactor bottom transferpump is set, and microorganism is leached reactor and connects the metal ion collector by transferpump.
Preferably, described microorganism is leached in the reactor and is provided with agitator.
Preferably, described metal ion collector is provided with the 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 simultaneously under the condition that nutritive substance lacks; Prussic acid preferentially leaches reactive metal, secondly is the inertia precious metal; After leaching the reaction end, pseudomonas can be decomposed remaining prussic acid, avoids secondary pollution.
The second, the void size of fine and close filter bed when guaranteeing that metal ion solution can leach smoothly, is stayed biological leach reactor in pseudomonad cells less than the pseudomonad cells size.
The 3rd, but slide plate is the dividing plate of both sides pulling, leaches reactor Yi Bian can make metal ion solution flow out microorganism smoothly after opening.
The 4th, the metal ion on-line monitoring system should be closed slide plate immediately in case monitor second metal ion species in the metal ion solution collector, guarantee the purity of metal ion solution in the metal ion solution collector, can eliminate metal component to the negative impact of the biological leaching rate of precious metal.
The 5th, the common metal ion that at first is dissolved out and pseudomonas thalline mixed solution flow in the metal ion collector under the effect of transferpump through the filtration of fine and close filter bed; Equipment metal ion on-line monitoring system in case monitor out second metal ion species, is closed slide plate in the metal ion collector, and a kind of metal ion solution extracted and finished this moment; With the output of the metal ion solution in the metal ion collector, obtain the higher single metal ion solution of purity; Repeat slide plate and open and the leaching leaching process of closing, can obtain the higher common metal of purity and precious metal single ionic solution successively; Metal ion in the solution can reclaim by the method for metal replacement.Reclaiming smashing waste circuit card precious metal with chemical method and physics method compares, the present invention has characteristics such as cost is low, efficient, pollution-free, has overcome that domestic employing physics method is difficult to reclaim the waste printed circuit board precious metal and chemical method can produce the shortcoming of serious secondary pollution.
Description of drawings
Fig. 1 realizes the biological apparatus structure synoptic diagram that leaches of smashing waste circuit card metal mixed particle precious metal of the present invention;
Among the figure: 1 is the bacterization entrance; 2 is the yeast culture device; 3 is transferpump; 4 are 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 the metal ion solution collector; 10 is the metal ion online monitoring system; 11 are the metal ion solution outlet.
Embodiment
Embodiment below in conjunction with example is further explained the present invention.
Embodiment 1
Smashing waste circuit card metal mixed particle precious metal bioleaching process is characterized in that, may further comprise the steps:
1. cultivate pseudomonas, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached produce the strongest state of prussic acid ability, to reach and produce the prussic acid ability the pseudomonas of strong state and the metal mixed particle that the smashing waste circuit card obtains after the high pressure static electricity sorting at room temperature react, pseudomonas secretes prussic acid, the metal mixed particle carries out metal and leaches reaction under the prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, secondly is the inertia precious metal;
2. the metal ion solution that leaches is obtained metal ion solution through fine and close depth filtration, deep bed filtration, the metal ion solution that filtration obtains is collected, in case monitor when having two metal ion species in the metal ion solution of collecting, stop the collection of metal ion solution at once, with the purity of the metal ion solution that guarantees to collect; 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) is obtained displaces common metal and precious metal respectively by the mode of metal replacement.
A kind of device of above-mentioned smashing waste circuit card metal mixed particle 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 by transferpump 3 and leaches reactor 4.Metal ion solution collector 9 connects metal ion online monitoring system 10.
Microorganism is leached reactor 4 and is provided with metal mixed particle input aperture 5.Microorganism is leached reactor 4 bottoms and is provided with fine and close filter bed 7.The void size of fine and close filter bed 7 is less than the pseudomonad cells size, and fine and close filter bed 7 bottoms are provided with slide plate 8.Slide plate 8 comprises two sheet materials, processing hollow slideway on one of them sheet material, and another sheet material one end is arranged in the hollow slideway and in the hollow slideway and moves around.Skateboard is two slide plates, Yi Bian be thinner entity hard slide plate, the other side is thicker hollow hard slide plate, and when slide plate need be opened, thinner slide plate can be received in the chamber of thicker hollow slide plate, to guarantee that leaching reactor bottom one side opens.
The microorganism corresponding with slide plate 8 leached reactor bottom transferpump 3 is set, and microorganism is leached reactor 4 and connects metal ion solution collectors 9 by transferpump 3.The transferpump delivery spout is connected on the leaching reactor wall of slide plate below, to guarantee that under the condition that slide plate is opened, the metal ion solution of outflow advances the transferpump delivery spout, is transported in the metal ion collector through after the fine and close filter bed filtration.
Microorganism is leached in the reactor 4 and is provided with agitator 6.
Metal ion solution collector 9 is provided with metal ion solution outlet 11.
At first pseudomonas is inoculated in the yeast culture device 2 by bacterization entrance 1, the substratum in the yeast culture device 2 is beef extract-peptone-sodium-chlor substratum; After in yeast culture device 2, cultivating for some time, make pseudomonas have the strongest product prussic acid ability (cultivating about 24 hours), by transferpump 3 the pseudomonas solution pump is gone into microorganism and leach in the reactor 4.
Simultaneously, by metal mixed particle input aperture 5 smashing waste circuit card metal mixed particle being joined microorganism leaches in the reactor 4; In microorganism was leached reactor 4, pseudomonas secreted prussic acid successively with the common metal in the metal mixed particle, precious metal dissolving, makes them become ionic state and enters in the solution.Under the condition that slide plate 8 one sides are opened, the common metal ion that at first is dissolved out and pseudomonas thalline mixed solution flow out microorganism and leach reactor 4 through the filtration of fine and close filter bed 7 under the effect of transferpump 3, flow in the metal ion solution collector 9.
Equipment metal ion on-line monitoring system 10 in case monitor out second metal ion species, should be closed slide plate 8 immediately in the metal ion solution collector 9, and a kind of metal ion solution extracted and finished this moment; Metal ion solution in the metal ion solution collector 9 is exported through delivery port 11, thereby obtained the higher single metal ion solution of purity; Repeat slide plate 8 and open and the leaching leaching process of closing, can obtain the higher common metal of purity and precious metal single ionic solution successively.Metal ion in the solution can reclaim by the method for metal replacement.
This method and apparatus can obtain the single ionic solution of various metals in the smashing waste circuit card, the various common metals 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 simultaneously under the condition that nutritive substance lacks; Prussic acid preferentially leaches reactive metal, secondly is the inertia precious metal; After leaching the reaction end, pseudomonas can be decomposed remaining prussic acid, avoids secondary pollution.
The void size of fine and close filter bed when guaranteeing that metal ion solution can leach smoothly, is stayed biological leach reactor in pseudomonad cells less than the pseudomonad cells size;
But slide plate is the dividing plate of both sides pulling, leaches reactor Yi Bian can make metal ion solution flow out microorganism smoothly after opening;
The metal ion on-line monitoring system should be closed slide plate immediately in case monitor second metal ion species in the metal ion solution collector, guarantee the purity of metal ion solution in the metal ion solution collector, can eliminate metal component to the negative impact of the biological leaching rate of precious metal.
The common metal ion that at first is dissolved out and pseudomonas thalline mixed solution flow in the metal ion collector under the effect of transferpump through the filtration of fine and close filter bed; Equipment metal ion on-line monitoring system in case monitor out second metal ion species, is closed slide plate in the metal ion collector, and a kind of metal ion solution extracted and finished this moment; With the output of the metal ion solution in the metal ion collector, obtain the higher single metal ion solution of purity; Repeat slide plate and open and the leaching leaching process of closing, can obtain the higher common metal of purity and precious metal single ionic solution successively; Metal ion in the solution can reclaim by the method for metal replacement.
Claims (4)
1. smashing waste circuit card metal mixed particle precious metal bioleaching process is characterized in that, may further comprise the steps:
1. cultivate pseudomonas, substratum is beef extract-peptone-sodium-chlor substratum, pseudomonas is reached produce the strongest state of prussic acid ability, to reach and produce the prussic acid ability the pseudomonas of strong state and the metal mixed particle that the smashing waste circuit card obtains after the high pressure static electricity sorting at room temperature react, pseudomonas secretes prussic acid, the metal mixed particle carries out metal and leaches reaction under the prussic acid effect, obtain metal ion solution, prussic acid preferentially leaches active common metal, secondly is the inertia precious metal;
2. the metal ion solution that leaches is obtained metal ion solution through fine and close depth filtration, deep bed filtration, the metal ion solution that filtration obtains is collected, in case monitor when having two metal ion species in the metal ion solution of collecting, stop the collection of metal ion solution at once, with the purity of the metal ion solution that guarantees to collect; 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) is obtained displaces common metal and precious metal respectively by the mode of metal replacement.
2. device of realizing the described smashing waste circuit card of claim 1 metal mixed particle precious metal bioleaching process, it is characterized in that, described device comprises yeast culture device, microorganism leaching reactor, metal ion collector, metal ion online monitoring system and transferpump, the yeast culture device connects microorganism by transferpump and leaches reactor, and the metal ion collector connects the metal ion online monitoring system; The yeast culture device is provided with the bacterization entrance; Microorganism is leached reactor and is provided with metal mixed particle input aperture, microorganism is leached reactor lower part and is provided with fine and close filter bed, the void size of fine and close filter bed is less than the pseudomonad cells size, fine and close filter bed bottom is provided with slide plate, described slide plate comprises two sheet materials, processing hollow slideway on one of them sheet material, another sheet material one end is arranged in the hollow slideway and in the hollow slideway and moves around; The microorganism corresponding with slide plate leached reactor bottom transferpump is set, and microorganism is leached reactor and connects the metal ion collector by transferpump.
3. the device of realization smashing waste circuit card metal mixed particle precious metal bioleaching process according to claim 2 is characterized in that, described microorganism is leached in the reactor and is provided with agitator.
4. the device of realization smashing waste circuit card metal mixed particle precious metal bioleaching process according to claim 2 is characterized in that, described metal ion collector is provided with the metal ion solution outlet.
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Cited By (6)
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| CN104726714A (en) * | 2013-09-30 | 2015-06-24 | 江苏理工学院 | Method for extracting copper out of waste printed circuit board by employing mixed bacteria |
| CN106011484A (en) * | 2016-07-08 | 2016-10-12 | 扬州大学 | Waste circuit board precious metal recovery device based on cyanogen generation bio-membrane reactor |
| CN107119194A (en) * | 2017-03-22 | 2017-09-01 | 中山大学 | The high-performance bio leaching method and device of a kind of waste and old circuit board noble metal |
| CN107746959A (en) * | 2017-11-17 | 2018-03-02 | 中山大学 | A kind of two step bioleaching process and device of total head recovery valuable metals in waste circuit board |
| EP3415647A1 (en) * | 2017-06-13 | 2018-12-19 | B.R.A.I.N. Ag | A process for recovering precious metals from secondary resources |
| 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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| CN104726714A (en) * | 2013-09-30 | 2015-06-24 | 江苏理工学院 | Method for extracting copper out of waste printed circuit board by employing mixed bacteria |
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| US11499205B2 (en) | 2017-06-13 | 2022-11-15 | Brain Ag | Process for recovering precious metals from secondary resources |
| JP7185646B2 (en) | 2017-06-13 | 2022-12-07 | ブレイン・アクチェンゲゼルシャフト | Methods of recovering precious metals from secondary resources |
| CN107746959A (en) * | 2017-11-17 | 2018-03-02 | 中山大学 | A kind of two step bioleaching process and device of total head recovery valuable metals in waste circuit board |
| 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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| CN103320619B (en) | 2015-05-20 |
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