CN101538651A - Method for recycling metal - Google Patents
Method for recycling metal Download PDFInfo
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- CN101538651A CN101538651A CN200910049738A CN200910049738A CN101538651A CN 101538651 A CN101538651 A CN 101538651A CN 200910049738 A CN200910049738 A CN 200910049738A CN 200910049738 A CN200910049738 A CN 200910049738A CN 101538651 A CN101538651 A CN 101538651A
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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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Abstract
The invention provides a method for recycling metal, comprising the following steps: 1. adding culture solution into a reaction kettle, inoculating strains into the reaction kettle for culturing at a constant temperature which ranges from 26 DEG C to 30 DEG C; 2. crushing metal waste into grains of 0.35-3mm to be put into the reaction kettle with the mass ratio of the metal waste and the culture solution being 1:5-1:20, and leaching the various metals in the metal waste; 3. carrying out solid-liquid separation to obtain metal waste grains and leaching solution; and 4. extracting the leaching solution to obtain concentrated solution and diluted solution. The obtained concentrated solution is evaporated to obtain CuSO4 with high purity; and the diluted solution can be used repeatedly as inoculating solution and culture solution in step 1 after being added with ferrous sulfate and inorganic salt. The method can effectively recycle the metals contained by PCB board of different natures, and is a technology which is environment-friendly and worthy of promoting.
Description
Technical field
The present invention relates to biotechnological means, be specifically related to a kind of method of utilizing microorganism to reclaim metal.
Background technology
Resource is the lifeblood of industry, and along with the minimizing of metals resources, regeneration, recycle electron wastes have become the important new problem of non-ferrous metal industry.Electron wastes has change and " gives up " and be precious great potential, but eco-friendly recovery is an electron wastes resource utilization regenerated difficult point, especially the high-value-use of the separating of the metal of discarded printed circuit boards and nonmetal basal body, polymetallic Separation and Recovery and non-metallic material is bottleneck problems of restriction China electron wastes resource treatment technique.
Nowadays, and world's printed circuit board (PCB) (Printed circuit board, PCB) Gong Ye average annual growth rate is 8.7%, the rate of increase of China is 14.4%.Up to the present, the PCB in the whole world about 40% produces in China.And the PCB basic component that to be electronic industry use from computer, televisor to simple electronic toy etc., all has PCB to exist in nearly all electronic product.China from 2003 annual a large amount of household appliances to scrap, computer and mobile phone renewal speed are scrapped the peak period and also will be arrived far faster than household appliances.Thereby the discarded PCB amount that needs to handle gets more and more.
Because the metal content among the PCB is higher than metal content in the common mineral far away, the content of metal is up to 40%, and maximum is copper, also has metals such as gold, aluminium, nickel, lead in addition.According to statistics, contain 129.8kg copper, 0.45kg gold, 40.9kg iron, 20kg nickel, 10kg antimony, 9kg silver and 0.1kg palladium approximately in circuit card that 1 ton (t) arbitrarily collects, wherein only the value of gold and palladium just above 8000 dollars.The metal content of China's rich ore only 3%～5%.In addition, both generally contained just like heavy metals such as Hg, As, Pb, Cd, Cr, Cu in the circuit card, also contained environmentally harmful materials such as brominated flame retardant, if handle with common solid waste, to cause unforeseen harm to environment, thereby be subjected to extensive concern.How to discard the resource utilization recycling of electron wastes such as PCB effectively, become a current new problem that is related to China's economy and environment sustainable development.In the comprehensive utilization of resources gordian technique country great industrial technology exploitation special project that National Development and Reform Committee organizes and implements, " printed circuit board (PCB) is recycled and innoxious process for treating " belongs to one of the focus development content of the 3rd " renewable resource comprehensive utilization technique ".
The processing method that reclaims metal among the PCB is more, after technical combinations such as pulverizing, magnetic separation, current vortex sorting, pneumatic separating, electrostatic separation, and metal ingredient among the recyclable PCB.The more PCB resource technology of research report has physics method, chemical method, burning method both at home and abroad in recent years, and wherein the physics method is divided into wet type and dry type again, and these methods respectively have its relative merits.Along with electronic product develops towards ultra-large integrated direction, make that metal component reaches the ideal liberation degree of minerals among the PCB, grinding particle size will be more and more littler.The thickness of copper-clad plate scope is 5～343 μ m at present, therefore requires disintegrating process to reach corresponding horizontal.But, in actual applications, reach the difficulty that tiny grinding particle size like this certainly will increase disintegrating process itself and follow-up separation technology, in fact high strength is pulverized in the PCB process and will be discharged toxic gas.This application that is also indicating above-mentioned processing PCB physics, method of chemical treatment is restricted, and microorganism leaching technology is less demanding to grinding particle size, estimate 1mm even bigger particle all can, break through the bottleneck of these traditional methods.Microbial method metal smelting technology is because of its environmental friendliness, the extensive concern that is subjected to low cost.
In sum, quickening at electronic product update speed, produce increasing discarded printed circuit boards, reclaim wherein contained metal and have higher industrial value and social effect, and the microorganism Wet-process metallurgy method relatively is suitable for reclaiming the metal in the PCB structure under the different production specifications.
Therefore, this area presses for the method that the development and use microorganism is reclaimed metal.
Summary of the invention
Purpose of the present invention just provides a kind of metal recovery processes.
A first aspect of the present invention provides a kind of metal recovery processes, comprises step:
(a) nutrient solution is added in the reactor, in reactor, constant temperature 26-30 degree is cultivated with bacterial classification inoculation, keeps stirring and ventilation;
(b) metal waste is pulverized to the 0.35-3.0 mm granules drops in the reactor, the mass ratio of metal waste and nutrient solution is 1: 5-1: 20, and the multiple metal in the leaching metal waste;
(c) carry out solid-liquid separation and obtain metal waste particle and leaching liquid;
(d) the extraction leaching liquid obtains concentrated solution and diluent.
Above-mentioned air flow is controlled at 0.5～0.75V/Vmin.
The mass ratio of above-mentioned metal waste and bacterium liquid is 1: 10 to 1: 20.
The volume ratio of bacterium liquid and nutrient solution is 1: 10 to 1: 20 in the above-mentioned steps (a).The volume ratio of preferred bacterium liquid and nutrient solution is 1: 10.
Above-mentioned bacterial classification is the ferrous thiobacillus of normal temperature oxidation.
The density of above-mentioned inoculation bacterial classification is 1 * 10
7Individual/ml-9 * 10
7Individual/ml.
Be provided with the agitator of self-priming band full angle blade in the aforesaid reaction vessel.
Above-mentioned stirring velocity is controlled at 120rpm/min～180rpm/min.
Be provided with heating system in the aforesaid reaction vessel.
Ceramic block is posted on aforesaid reaction vessel internal layer surface.
Above-mentioned metal recovery processes also comprises the steps:
(e) reextraction concentrated solution obtains copper-bath.
Above-mentioned metal recovery processes also comprises the steps:
(e) electrolysis concentrated solution obtains copper.
After diluent in the above-mentioned steps (d) is added an amount of ferrous sulfate and inorganic salt, can be repeatedly as inoculation liquid in step (a).
Above-mentioned ferrous sulfate (FeSO
4) concentration is: 10～40g/L.
Above-mentioned inorganic salt are (NH
4)
2SO
4: 0.15～3.0g/L, K
2HPO
4: 0.05～0.5g/L, MgSO
47H
2O:0.05～0.5g/L, KCl:0.05～0.5g/L, Ca (NO
3)
2: 0.01～0.1g/L.
Above-mentioned metal recovery processes also comprises step:
(f) other metals in the high-speed counter-current abstraction instrument extracting and separating diluent.
Preferable, detect the content of Sn in the diluent, as Sn during more than or equal to 2g/L, implementation step (f).
Above-mentioned other metals are Cr, Ni, Zn, Ag, Au or Sn etc.Preferable, behind repeating step (a) to (d) 3 times-6 times, implementation step (f).
The described separation method of above-mentioned steps (c) is for being centrifuging.Preferred bag-turning pattern whizzer carries out centrifugal.
Above-mentioned steps (a) adopts improved Leathen liquid nutrient medium or 9K substratum.The Leathen liquid nutrient medium of advantageous embodiment.
Preferable, above-mentioned Leathen liquid nutrient medium consists of: A liquid, (NH
4)
2SO
4: 0.15～3.0g/L, K
2HPO
4: 0.05～0.5g/L, MgSO
47H
2O:0.05～0.5g/L, KCl:0.05～0.5g/L, Ca (NO
3)
2: 0.01～0.1g/L, pH value 1.5-2.5, ferrous sulfate: 10～40g/L.General sulfuric acid or the hydrochloric acid of using is regulated pH value.Preferably sulfuric acid.
The preferred 10-40g/L of ferrous sulfate concentration in the above-mentioned Leathen liquid nutrient medium.
Incubation time is 7-12 days in the above-mentioned steps (b).
The present invention is directed to and be about to a large amount of discarded PCB and need to handle, propose the method that a kind of microorganism is leached metals such as Cu among the PCB, this method can leach metal among the PCB of different nature effectively, by the electrolysis leach liquor, finally can obtain the various metals of high purity.
The agitator (see figure 4) of self-priming band full angle blade of the present invention is by guide shell bubbling air in leaching liquid, and the full angle blade has two kinds of functions when stirring: 1. stirring makes the repeating dispersion of PCB particle in leaching liquid, and can avoid the PCB particle to be adsorbed on the wall of reactor; 2. stir and driven air and mix, make bacterial classification can obtain competent oxygen with leaching liquid.
Technical solution of the present invention is: screen, be separated to thiobacillus ferrooxidant (Acidthiobacillus ferrooxidans from the mud mixture that gather the discarded ore storage bottom of China's copper mine, hereinafter to be referred as the T.f bacterium), bacterium liquid after the domestication is preserved, and is standby; PCB pulverizes on pulverizer, control grain graininess＜3mm.In the reactor of microorganism leaching PCB, add inoculation liquid and substratum earlier, open heating system, keep that solution temperature is 28 ± 2 ℃ of constant temperature in the reactor, cultivate 1d in advance after, at the discarded pcb board particle (solid-to-liquid ratio=1: 5～1: 20) that stirs after adding an amount of the pulverizing under the stop condition not.Continuously stirring, ventilation, what stir to adopt is the full angle agitating vane, and the blade bottom interval and is had scraping article, and the scraping article bottom is apart from the about 1cm of reactor bottom intermittence, and speed is controlled in 90rpm/min～150rpm/min scope during stirring; Ventage arranges that along whole reactor vertical direction inwall every interval 5cm opens a ventilating pit on the ventpipe, and bacterial classification leaching PCB goes up in the metal process, uninterruptedly ventilates in reactor, and air flow is controlled in 0.5～0.75V/Vmin scope.Thereby guarantee that the PCB particle can be suspended in the solution fully, and not overlapping between particle, and allow bacterial classification can fully obtain oxygen, improve leaching efficiency.Behind the reaction 4d, in reaction solution, add the energy substance ferrous sulfate of bacterial classification.Continue to leach, behind cultivation 7～10d, open the valve of reactor bottom, stirring under the uninterrupted condition, the leach liquor that contains PCB particle residue is shifted out reactor, the sand core funnel through being lined with industrial filter cloth is cast out filter residue after filtering, and obtains the metal leach liquor.Get this solution example a little, measure wherein contained metal ion content, calculate PCB and go up the metal solubility rate.After surplus solution concentrated through extraction (extraction agent is RE609), concentrated solution directly entered electrolysis in the electrolyzer, obtains high-purity copper, perhaps looks market situation, behind the direct evaporate to dryness of concentrated solution, obtained high-purity C uSO
4Contain the bacterium dilute solution after the extraction, pump into again in the reactor, after adding an amount of ferrous sulfate and improving A liquid in the Leathen substratum, can continue with being to leach the reaction solution that PCB goes up metal as inoculation liquid; After so repeatedly more than 3 times, bullion contents such as the Au that contains in the dilute solution, Ag raise, and this dilute solution is therefrom separated noble metals such as Au, Ag through counter current chromatograph, obtain the vitriol of precious metals such as Au, Ag.
The present invention compared with prior art, microbial method can leach metals such as Cu, Pb, Zn, Ni effectively from the variable grain of various Property P CBs, dilute solution after concentrating can continue on for leaching PCB as microbial inoculant liquid and go up metals such as Cu, can not bring secondary pollution; After the first step extraction, electrolysis can obtain the Cu of 99% above purity; After the dilute solution repeated multiple times was used for extracting, dilute solution was through counter current chromatograph, the vitriol of noble metals such as the highly purified Au of separable acquisition, Ag; This method is with low cost, and environmental friendliness has actual popularization proper value.
The printed circuit board (PCB) particle of preparation copper-clad plate, the copper-clad plate that contains green oil, the multiple electric equipment products of depleted is pulverized on pulverizer earlier, crosses vibratory screening apparatus.The standard sieve screen size of selecting for use has 3.00mm, 1.00mm, 0.75mm, 0.50mm, 0.35mm, PCB particle on the different sieves carries out packing, abundant mixing before packing, guarantee uniformity of sample, amount to 6 kinds of particles, be respectively:＜0.35mm, 0.35-0.50mm, 0.50-0.75mm, 0.75-1.00mm, 1.00-3.00mm,＞3.00mm.According to metal content in economic benefit of pulverizing and the particle, with pulverize the moderate 1.00-3.00mm particle of economical and efficient, metal content and metal content is higher, pulverize the high slightly 0.50-1.00mm particle of cost be bacterial classification leaching PCB go up the metal efficient studies for the examination particle.The various particles that make are standby.
Configuration Leathen substratum takes by weighing above-mentioned PCB particle of different nature, sterilization.Inoculate the bacterium liquid after the above-mentioned domestication, vibration leaching PCB particle can leach the metal on the various PCB effectively on constant temperature oscillator.Leach liquor is by extracting and separating, and electrolysis can obtain highly purified Cu.And the bacterium liquid (being diluent) that contains after the extraction inoculates in the new leach liquor, can continue to leach PCB and go up metal.
Bacterial classification by the present invention's screening can leach metals such as Cu, Pb, Zn, Ni efficiently from the variable grain of various Property P CB.And the dilute solution after the extraction can continue on for leaching metals such as the last Cu of PCB as microbial inoculant liquid, can not bring secondary pollution.And through the experiment over 2 years, this bacterial classification stable performance can continue to be used to leach PCB and go up metal.
Others of the present invention are because disclosing of the technology of this paper is conspicuous to those skilled in the art.
Below in conjunction with embodiment the present invention is described in further detail.
Description of drawings
Fig. 1 is the technology of the present invention route map.
Fig. 2 is the influence of Cu leaching rate in the copper-clad plate handled of the T.f bacterium B of normal temperature (28 ℃).
Fig. 3 is the influence that contains Cu leaching rate in the green oil copper-clad plate that the T.f bacterium A of normal temperature (28 ℃) handles.
Fig. 4 is a propeller-blade synoptic diagram in the leaching vat.
Fig. 5 is the efficient that the T.f bacterium is leached multiple metal.
Fig. 6 is the efficient that the T.f bacterium is leached Cu in the 1.00-3.00mm PCB particle.
Fig. 7 is the extraction process synoptic diagram of leach liquor.
1. extraction agent storage tank; 2. leaching liquid storage tank; 3. raffinate liquid pool; 4. reextraction mixer-settler; 5. extraction liquid pool; 6. water liquid stores up the pond; 7. electrolytic solution stores up the pond; 8. poor electrolytic solution storage pond; 9. electrolyzer; 10. electrolyzer; 11. extraction mixer-settler; 12 cotton filters
Fig. 8 is the efficient that the T.f bacterium is leached Cu in the 0.50-1.00mm PCB particle.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to people such as normal condition such as Sambrook, molecular cloning: laboratory manual (NewYork:Cold Spring Harbor Laboratory Press, 1989) condition described in, or the condition of advising according to manufacturer.Reagent of unreceipted businessman or manufacturer etc. is the commercially available prod among the present invention.
1 sample collecting
The samples such as ore mud that deposit in the flotation fluid that discharge in soil and flotation workshop the green belt of doorway, flotation workshop in pit waste water and bed mud thereof, discarded ore storage bottom mud mixture, mining area are gathered in China copper mine mining area, measure the pH value and the contained various metal element content of these samples in the laboratory earlier, pick out metal content height (Cu＞3.0gkg
-1Pb＞0.5gkg
-1Cd＞0.2gkg
-1Cr＞0.5gkg
-1Sn＞0.3gkg
-1Zn＞1.5gkg
-1), the sample of pH value lower (PH1.5-2.5), from this sample, carry out following operation, screening target bacterial classification.
2 screening methods
Pre-configured improved Leathen liquid nutrient medium, substratum consists of (unit is g/L): A liquid, (NH
4)
2SO
40.15, K
2HPO
40.05, MgSO
47H
2O 0.05, and KCl 0.05, Ca (NO
3) 20.01, pH value 2.5; B liquid, ferrous sulfate 30.46, filtration sterilization.Get the A liquid 45ml for preparing in the 150ml triangular flask, 121 ℃ of moist heat sterilizations; Treat that the A liquid cooling but adds B liquid 5ml in the back, mixing is standby.
Take by weighing each 5g of 2 duplicate samples in 2 liquid nutrient mediums (PH2.5, PH1.5) in, shaking culture in 28 ℃ of following constant temperature oscillators is transferred to respectively after one week in the new liquid nutrient medium, continue to cultivate 3 times so repeatedly.Separate bacterial classification from liquid nutrient medium, method after the coating evenly, is cultivated a week for drawing the 0.5ml liquid medium on the Leathen solid medium, and line separates, and obtains pure bacterium colony.
3 acclimation methods
The bacterial classification inoculation that screens in the aforesaid liquid substratum, and is added 1cm through the alcohol sterilization
2The ability whether bacterial classification has metal in the leaching copper-clad plate is observed in copper-clad plate; Constantly increase the copper-clad plate amount (0.5-20g) that adds, when domesticated strain leached the ability of metal among the PCB, also domesticated strain tolerated the ability of high density metal.Final acquisition can efficiently leach the bacterial classification A that PCB goes up metal (28 ℃, PH2.5), B (28, ℃ PH1.5).
Cu experiment on the copper-clad plate particle of the high metal content of embodiment two normal temperature T.f bacterium (B) leaching
2.1 granules preparation
Copper-clad plate particulate preparation: in pulverizer (valiant horse machinery Shanghai company limited, model GSC) the PCB particle of going up after pulverizing is crossed standard sieve, the standard sieve screen size of selecting for use has 0.50mm, 1.00mm, copper-clad plate particle on the different sieves carries out packing, abundant mixing before packing, guaranteeing uniformity of sample, is for the examination particle with 0.50-1.00mm.
2.2 experimental design
The liquid nutrient medium of T.f bacterium is that improved Leathen substratum is formed (g/L): A liquid, (NH
4)
2SO
40.15, K
2HPO
40.05, MgSO
47H
2O 0.05, and KCl 0.05, Ca (NO
3)
20.01, pH value 2.5, moist heat sterilization; B liquid, ferrous sulfate 15, filtration sterilization; Treat that the A liquid cooling but adds B liquid in the back, mixing is standby.Above-mentioned culture medium A liquid packing 45ml takes by weighing the various particles after 0.5g pulverizes in the 150ml triangular flask, at 115 ℃ of 20min that sterilize down.After the cooling, the B liquid 5ml behind the adding filtration sterilization.(by measure turbidity on spectrophotometer, the control inoculum density is about 9 * 10 to inoculation domestication back T.f (B) bacterium liquid 1ml
7Individual/ml), all inoculation liquid are shaking culture in 28 ℃ of constant-temperature shaking culture devices, and the contrast of not inoculating is cultivated together.
Above-mentioned processing places 28 ℃ of vibrations of constant-temperature shaking culture case (120rpm/min) to cultivate 9d respectively.
2.3 measuring method
Earlier with chloroazotic acid (HCl: HNO
3=3: 1) digest 2h in 100ml long-neck triangular flask, heating up is evaporated near doing, and adds distilled water post-heating Hui Rong.Again repeatedly, be transferred in the 20ml scale test tube constant volume with distilled water wash.Use Cu content in inductively coupled plasma emission spectrometer (ICP-AES) (the U.S. Thermo A6300 type) working sample immediately.
2.4 result
From 1 day to 3 days, the leaching rate Cu leaching yield of Cu rose comparatively fast in the copper-clad plate that inoculation normal temperature T.f bacterium B handles, and reaches 65% from 18%, until 9 days the time, almost all strippings (Fig. 2) of Cu in the copper-clad plate.As seen, the bacterial classification by the inventive method screening can leach Cu in the copper-clad plate efficiently.
Embodiment three normal temperature T.f bacterium A leach and contain metal experiment in the green oil copper-clad plate
3.1 granules preparation
Contain green oil copper-clad plate granules preparation: the PCB particle after pulverizing on the pulverizer is crossed standard sieve, and the particle of selecting the higher 0.50-1.00mm of metal content for use is for supplying the examination particle.
3.2 experimental design
With 2.2.
Cu content in the sampling analysis solution behind the cultivation 9d.
3.3 measuring method
With 2.3
3.4 result
As shown in Figure 3, begin to end, singly connect the solubility rate that contains Cu in the green oil copper-clad plate that T.f handles and raise gradually, contain Cu leaching yield in the green oil copper-clad plate and rise to 92% from initial 25% from cultivation.The result shows that the last green oil of PCB can not hinder bacterial classification and leach the Cu that contains in the green oil copper-clad plate effectively.
The discarded PCB of reality that embodiment four normal temperature T.f bacterium A leach variable grain goes up the metal experiment
4.1 granules preparation
Actual discarded PCB granules preparation: the PCB particle after pulverizing on the pulverizer is crossed standard sieve, the standard sieve screen size of selecting for use has 3.00mm, 1.00mm, 0.75mm, 0.50mm, 0.35mm, copper-clad plate particle on the different sieves carries out packing, abundant mixing before packing, guarantee uniformity of sample, amount to 6 kinds of particles, be respectively:＜0.35mm, 0.35-0.50mm, 0.50-0.75mm, 0.75-1.00mm, 1.00-3.00mm,＞3.00mm.
4.2 experimental design
With 2.2.
The sampling analysis GOLD FROM PLATING SOLUTION belongs to content after cultivating 5d.
4.3 mensuration project
The treatments of the sample method is with 2.3.Measure metal and mainly contain Cu, Cr, Ni, Zn, Au, Ag, Sn etc.
4.4 result
As shown in Figure 5, the discarded PCB that the T.f bacterium A by the inventive method screening can leach variable grain goes up multiple metal, and because of the granular size difference, the leaching yield of various metals is not quite similar.Along with particle diminishes, the last Cu leaching yield of PCB increases gradually, is respectively 42.4,50.2,80.1,82.6,86.7,88.6%; And Cr, Ni, Zn, Au, metals such as Ag, Sn all have leaching (see figure 5) in various degree on the PCB.This shows, the bacterial classification by the present invention's screening not only can leach the Cu on the variable grain size efficiently, and can leach other metallic element beyond the Cu.
Embodiment five bacterial classification A are to the leaching efficiency of Cu in 1.00～3.00mmPCB particle
Materials and methods
T.f bacteria liquid substratum is formed (amount of reagent that adds among every 1000ml): (NH
4)
2SO
4, 0.15g/L, K
2HPO
4, 0.05g/L, MgSO
47H
2O:0.05g/L, KCl:0.05g/L, Ca (NO
3)
2: 0.01g/L, ferrous sulfate: 40g, the pH value is 2.5; The solution that configures is unsterilised.The bacterial strain T.f bacterium of 3d, cell density 9 * 10 are cultivated in inoculation in advance with liquid culture method
7Individual/ml.
According to solid-to-liquid ratio (mass ratio) is 1: 20, and the PCB particle that takes by weighing 10kg 1.00 ~ 3.00mm does not stir in reactor and to add the PCB particle under the stop condition in above-mentioned substratum 200L, and the T.f bacterium liquid 20L that inoculation culture is good cultivates 10d.Above-mentioned processing collected specimens every day 5ml, each 3 bottles, gather 10d altogether, amount to 30 bottles.When collected specimens can not in time be analyzed, place 4 ℃ of refrigerators to preserve earlier.
The sample of gathering is earlier with chloroazotic acid (HCl: HNO
3=3: 1) digest 2h in 100ml long-neck triangular flask, hot digestion is closely dried to solution, adds distilled water post-heating Hui Rong.Again repeatedly, be transferred in the 20ml scale test tube constant volume with distilled water wash.Use the content of Cu and other metal in inductively coupled plasma emission spectrometer (ICP-AES) working sample immediately.
The trend that the solubility rate of Cu rises gradually in the copper-clad plate particle that inoculation T.f bacterium is handled, from 1d 11% to 10d about 90%, average every day, the leaching rate with about 9% increased (see figure 6).By the Cu in the earlier concentrated leach liquor of extraction process, detailed process is a (see figure 7): the leach liquor input extraction mixer-settler after cotton filter filters, from the extraction agent storage tank, feed extraction agent, and stir, leave standstill, obtain organic phase and water, water input raffinate liquid pool; Organic phase is then imported the reextraction mixer-settler, further obtains water and organic phase, and water directly moves into water liquid storage pond,, needs to filter through cotton filter with pump when electrolytic solution stores up the pond input, progressively puts into electrolyzer and carries out electrolysis acquisition metal Cu; Organic phase then enters the extraction liquid pool, pumps in the reextraction mixer-settler to strip again.Poor electrolytic solution after the electrolysis feeds poor electrolytic solution storage pond, accumulated a certain amount of poor electrolytic solution after, pump into again in the reextraction mixer-settler and strip.So repeatedly, promptly after the extraction of leach liquor process, the reextraction system, obtain high-concentration sulfuric acid copper concentrated solution, after the evaporation drying, obtain purity and reach 98% copper sulfate.
Dilute solution be used for circulation leaching PCB go up metal back more than 2 times (because of metal content on the circuit card variant, concrete number of times is seen metal concentrations such as Cr in the leaching liquid, Ni, Zn, Ag, Au, Sn or Pb, it generally is benchmark with Sn, in solution, reach 2g/L when above, after separating these metallic elements, leaching liquid is reuse again), diluent after will extracting again is by high-speed counter-current abstraction instrument (Shanghai Tongtian Biotechnology Co., Ltd., model HSCCC-TBE300) extraction Cr, Ni, Zn, Ag, Au or Sn wherein.
Embodiment six bacterial classifications are to the leaching efficiency of Cu in 0.35 ~ 1.00mmPCB particle
Materials and methods
The T.f bacterium is cultivated with example 1.
According to solid-to-liquid ratio is 1: 10 (mass ratio), and the PCB particle that takes by weighing 20kg 1.00 ~ 3.00mm does not stir in reactor and to add the PCB particle under the stop condition in above-mentioned substratum 200L, and the T.f bacterium liquid 20L that inoculation culture is good cultivates 10d.Above-mentioned processing collected specimens every day 5ml, each 3 bottles, gather 10d altogether, amount to 30 bottles.When collected specimens can not in time be analyzed, place 4 ℃ of refrigerators to preserve earlier.
Sample treatment is with embodiment five.
The leaching rate of Cu changes differently along with the prolongation of time in the copper-clad plate that inoculation T.f handles, and from 1d to 4d, the Cu leaching yield rises very fast, reaches 49% from 18%, and metal leaches half near total metal contents in soil, and during to 9d, the last Cu leaching yield of PCB reaches 94.8%.Behind extraction of leach liquor process and the reextraction groove, electrolysis obtains purity and reaches 99% Cu (see figure 8).
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1, a kind of metal recovery processes is characterized in that, comprises step:
(a) nutrient solution is added in the reactor, in reactor, ventilation, constant temperature 26-30 degree are cultivated with bacterial classification inoculation;
(b) metal waste is pulverized to the 0.35-3 mm granules drops in the reactor, the mass ratio of metal waste and nutrient solution is 1: 5-1: 20, and the multiple metal in the leaching metal waste;
(c) carry out solid-liquid separation and obtain metal waste particle and leaching liquid;
(d) the extraction leaching liquid obtains concentrated solution and diluent.
2, the described metal recovery processes of claim 1 is characterized in that, described air flow is 0.5～0.75V/Vmin.
3, the described metal recovery processes of claim 1 is characterized in that, the mass ratio of described metal waste and bacterium liquid is 1: 10 to 1: 20.
4, the volume ratio of bacterium liquid and nutrient solution is 1: 10 to 1: 20 in claim 1 step (a).
5, the described metal recovery processes of claim 1 is characterized in that, is provided with the agitator and the heating system of self-priming band full angle blade in the described reactor.
6, the described metal recovery processes of claim 5 is characterized in that, ceramic block is posted on described reactor internal layer surface.
7, the described metal recovery processes of claim 1 is characterized in that, described metal recovery processes also comprises the steps:
(e) electrolysis concentrated solution obtains copper; Or the reextraction concentrated solution, obtain copper-bath.
8, the described metal recovery processes of claim 1 is characterized in that, after the diluent in the described step (d) is added an amount of ferrous sulfate and inorganic salt, can be used as the inoculation liquid in the step (b) repeatedly.
9, the described metal recovery processes of claim 8 is characterized in that, described metal recovery processes also comprises the steps:
(f) other metals in the high-speed counter-current abstraction instrument extracting and separating diluent.
10, the described metal recovery processes of claim 9 is characterized in that, described other metals are Cr, Ni, Zn, Ag, Au or Sn.
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