CN106555055A - The system and method for solid metallic is reclaimed from waste liquid containing metal - Google Patents
The system and method for solid metallic is reclaimed from waste liquid containing metal Download PDFInfo
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- CN106555055A CN106555055A CN201510633876.4A CN201510633876A CN106555055A CN 106555055 A CN106555055 A CN 106555055A CN 201510633876 A CN201510633876 A CN 201510633876A CN 106555055 A CN106555055 A CN 106555055A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
A kind of system that solid metallic is reclaimed from waste liquid containing metal, including a waste liquid temporary storage location, one extraction cells and an electrolysis cells, the waste liquid temporary storage location is used to keep in a waste liquid containing metal, the extraction cells are connected with the waste liquid temporary storage location, the extraction cells include an extraction equipment and a back extraction device, wherein the extraction equipment is used to collect the metal ion in the waste liquid containing metal, the back extraction device for by collected by the extraction equipment the metal ion back extraction is into a strip liquor and forms a metallic compound, the electrolysis cells are connected with the waste liquid temporary storage location and the extraction cells, for the metal ion in the waste liquid containing metal is directly reduced to a solid metallic, or the metallic compound in the strip liquor dissociates and separates out to obtain the solid metallic.
Description
Technical field
The present invention relates to metals resources regeneration techniques, particularly relates to one kind and reclaims solid-state from waste liquid containing metal
The system and method for metal.
Background technology
With the progress of electronics industry, for example general consumer household electrical appliances of electrically or electronically device of difference in functionality
And 3C Product etc., manufactured in a large number, sold and widely used.And it is this kind of electrically or electronically in manufacture
In the related plating industry of device or circuit manufacturing industry, the waste liquid of a large amount of tool contaminatives can be usually produced,
Especially acid pickle.
Acid pickle generally comprises the phosphoric acid with recoverable value, acetic acid, nitric acid or sulfuric acid, or even
It is useful metal, such as copper or nickel.Therefore, in the prior art, often using various recycling sides
Formula is reclaiming acid solution therein and metal.For example, reducing metal ingredient therein using plating mode becomes
Metallic state, but organic efficiency can be affected in reduction treatment because of the reduction of tenor in waste liquid and is returned
Receive the quality of metal, it is therefore desirable to timing detection tenor, and supplement waste liquid, when causing practical operation
Need substantial amounts of manpower.Additionally, the recovery of acid solution usually utilizes heating distillation mode to return in acid pickle
Acid solution of the boiling point compared with low temperature, nitric acid of the such as boiling point less than sulfuric acid are received, but the high sulfuric acid of boiling point then needs
Extra reclaimer is processed.Especially, the recovery of metal and the recovery of acid solution is returned by different independence
Receipts system is carried out, and more causes the complexity of processing procedure, and cost recovery to increase.
Accordingly, it would be desirable to a kind of waste acid recovery system, there is provided the acid solution of high integration and metal recovery are processed,
The complexity reduces cost for reclaiming processing procedure can be simplified, and then solve above-mentioned problem of the prior art.
The content of the invention
The present invention from metals resources recycling with mitigate carrying capacity of environment angle, main purpose
One is to provide a kind of system and method that solid metallic is reclaimed from waste liquid containing metal, and which not only has economy
Contained metal ingredient in benefit and the comprehensive Recycling of waste liquid of energy, it is often more important that the metal purity for being reclaimed is high
And recycling property is good.
For achieving the above object, the present invention is employed the following technical solutions：One kind is reclaimed from waste liquid containing metal
The system of solid metallic, including a waste liquid temporary storage location, an extraction cells and an electrolysis cells.The waste liquid
Temporary storage location is used to keep in a waste liquid containing metal, and the extraction cells are connected with the waste liquid temporary storage location, the extraction
Taking unit includes an extraction equipment and a back extraction device, and the wherein extraction equipment contains metal for collecting this
A metal ion in waste liquid, the back extraction device is for by the metal ion collected by the extraction equipment
Back extraction is into a strip liquor and forms a metallic compound, the electrolysis cells and the waste liquid temporary storage location and
The extraction cells are connected, for the metal ion in the waste liquid containing metal is directly reduced to solid-state gold
Category, or the metallic compound in the strip liquor is dissociated and separates out to obtain the solid metallic.
According to an embodiment of the present invention, wherein the extraction equipment is via a strip liquor circulation line and is somebody's turn to do
Back extraction device is interconnected, the strip liquor circulation line further via an electrolysis cells entrance pipe with
The electrolysis cells are interconnected, and the waste liquid temporary storage location is also via the electrolysis cells entrance pipe and the electrolysis
Unit is interconnected.
One top discharge end of another embodiment of the invention, wherein the waste liquid temporary storage location with should
One top entry end of extraction equipment is interconnected, and the strip liquor circulation line includes that a first direction is conveyed
Pipe and a second direction delivery pipe, and a top discharge end of the extraction equipment is conveyed via the first direction
Pipe is interconnected with a top entry end of the back extraction device, and a bottom inlet end of the extraction equipment
It is interconnected via a bottom discharge end of the second direction delivery pipe with the back extraction device.
Another embodiment of the invention, wherein the electrolysis cells entrance pipe include that one is useless containing metal
Liquid delivery pipe, a strip liquor delivery pipe and an electrolysis cells inlet tube, a bottom of the waste liquid temporary storage location
Discharge end connects one end of the electrolysis cells inlet tube via the delivery pipe of waste liquid containing metal, and the electrolysis list
The other end of first inlet tube is connected to a top entry end of the electrolysis cells, and the strip liquor delivery pipe connects
Between a ramification point and the electrolysis cells inlet tube of the second direction delivery pipe.
Another embodiment of the invention, wherein the waste liquid temporary storage location, the extraction equipment and the electricity
Solution unit connects a factory service end via one discharging of waste liquid/recovery pipe.
Another embodiment of the invention, the wherein discharging of waste liquid/recovery pipe include one first waste liquid
Delivery pipe, one second discharging of waste liquid pipe, one the 3rd waste liquid delivery pipe and at least one the 4th discharging of waste liquid pipe,
Another bottom discharge end of the waste liquid temporary storage location connects the factory service end via the first discharging of waste liquid pipe, should
Second discharging of waste liquid pipe is arranged in a ramification point and the first discharging of waste liquid pipe of the delivery pipe of waste liquid containing metal
Between, another bottom discharge end of the back extraction device via the 3rd waste liquid delivery pipe sequentially connect this
Two discharging of waste liquid pipes and the first discharging of waste liquid pipe, and an at least discharge end of the electrolysis cells is via at least
One the 4th discharging of waste liquid pipe connects the first discharging of waste liquid pipe.
Another embodiment of the invention, further includes a deployment unit, the deployment unit and the back extraction
Take device and the electrolysis cells are connected, for reclaiming back extraction Jing after electrolysis that the electrolysis cells are discharged
Liquid, and the new strip liquor is supplied to the back extraction device.
Another embodiment of the invention, the wherein deployment unit include a chemical raw material groove and sour
Base number adjustment tank, a bottom discharge end of the chemical raw material groove connect the pH-value via a medicament delivery pipe
One top entry end of adjustment tank, and a bottom discharge end of the pH-value adjustment tank is via a pharmaceutical supply
Pipe connects another top entry end of the back extraction device.
Another embodiment of the invention, the wherein discharging of waste liquid/recovery pipe further include a waste liquid and return
Closed tube, a discharge end of the electrolysis cells connect the another of the pH-value adjustment tank via the devil liquor recovery pipe
Top entry end.
Another embodiment of the invention, further includes a water service source and an air supplies,
The water service source connects the another top entry of the pH-value adjustment tank via a running water delivery pipe
End, the air supplies connect an air input of the electrolysis cells simultaneously via an air delivery pipe
With an air input of the pH-value adjustment tank.
A concentration detector is provided with another embodiment of the invention, wherein the waste liquid temporary storage location,
For detecting the metal concentration containing metal waste liquid.
According to said system, the present invention separately provides a kind of method that solid metallic is reclaimed from waste liquid containing metal,
Comprise the following steps：First, a waste liquid containing metal is extracted, is contained metal waste liquid to isolate this
In a metal ion；Then, contacted with the metal ion using a strip liquor, make the metal from
A rich metal extraction liquid is formed during son is transferred to the strip liquor；Finally, the rich metal extraction liquid is carried out
Electrolysis, to obtain a solid metallic.
According to an embodiment of the present invention, wherein it is described a waste liquid containing metal is extracted the step of
Before, methods described also includes importing a waste liquid containing metal and is kept in one waste liquid temporary storage location.
Another embodiment of the invention, wherein it is described will a waste liquid containing metal import a waste liquid it is temporary
Further include during temporary step is carried out in memory cell and detect the metal concentration containing metal waste liquid.
Another embodiment of the invention, wherein it is described will a waste liquid containing metal import a waste liquid it is temporary
Temporary step is carried out in memory cell and it is described the step of a waste liquid containing metal is extracted before between, institute
State method also to comprise the following steps：The testing result of the metal concentration of metal waste liquid is contained according to this, and it is pre-
First a high concentration metal waste liquid is electrolysed, to reclaim the gold of the high concentration in the high concentration metal waste liquid
Category；And the high concentration metal waste liquid Jing after being electrolysed is imported kept in the waste liquid temporary storage location.
Another embodiment of the invention, the wherein strip liquor are hydrochloric acid.
The present invention also provides a kind of method that solid metallic is reclaimed from waste liquid containing metal, including following step
Suddenly：First, there is provided a waste liquid containing metal, this contains metal waste liquid comprising one first metal ion and one second
The concentration of metal ion, the wherein concentration of first metal ion higher than second metal ion；Then,
The waste liquid containing metal is extracted, with second metal ion being previously isolated from out in the waste liquid containing metal；
Then, this Jing after extracting is contained metal waste liquid to be electrolysed, to obtain corresponding to first metal ion
One first solid metallic, and while contacted with second metal ion using a strip liquor, make this
A rich metal extraction liquid is formed during second metal ion is transferred to the strip liquor；Finally, by the rich metal
Extract is electrolysed, to obtain one second solid metallic corresponding to second metal ion.
The present invention has clear advantage and has the beneficial effect that compared with prior art：The system of the present invention/
Waste liquid temporary storage location, extraction cells and electrolysis cells are connected with each other by method through the pipeline of particular design
Together, can the concentration of metal ingredient and selecting according to contained by waste liquid first extracted/back extraction is then electrolysed
Processing mode or be first electrolysed the processing mode of then extraction/back extraction, and then returning for metal can be greatly improved
Yield, and effectively extend electrolysis cells in substrate (battery lead plate) and the resin in extraction equipment use
Life-span.
Other objects of the present invention and advantage can be obtained further from technical characteristic disclosed in this invention
Understand.It is in order to the above and other objects, features and advantages of the present invention can be become apparent, hereafter special
For embodiment and coordinate appended by accompanying drawing be described in detail below.
Description of the drawings
Squares of the Fig. 1 for the system that solid metallic is reclaimed from waste liquid containing metal of first embodiment of the invention
Figure.
Frameworks of the Fig. 2 for the system that solid metallic is reclaimed from waste liquid containing metal of first embodiment of the invention
Figure.
Squares of the Fig. 3 for the system that solid metallic is reclaimed from waste liquid containing metal of second embodiment of the invention
Figure.
Frameworks of the Fig. 4 for the system that solid metallic is reclaimed from waste liquid containing metal of second embodiment of the invention
Figure.
Fig. 5 is a kind of stream of embodiment of method that solid metallic is reclaimed from waste liquid containing metal of the present invention
Journey schematic diagram.
Fig. 6 is the method another embodiment that solid metallic is reclaimed from waste liquid containing metal of the present invention
Schematic flow sheet.
Fig. 7 is method another embodiment of recovery solid metallic from waste liquid containing metal of the present invention
Schematic flow sheet.
【Symbol description】
S, S ' system
1 waste liquid temporary storage location
1a top discharges end
1b bottom discharges end
1c bottom discharges end
11 concentration detectors
2 extraction cells, 23 strip liquor circulation line
21 extraction equipment, 231 first direction delivery pipe
232 second direction delivery pipe of 21a top entries end
21b top discharges end
21c bottom inlets end
22 back extraction devices
22a top entries end
22b bottom discharges end
22c bottom discharges end
22d top entries end
3 electrolysis cells, 31 electrolysis cells entrance pipe
3a top entries end
3b discharge ends
3c air inputs
311 pipes of discharging of waste liquid containing metal
312 strip liquor delivery pipes
313 electrolysis cells inlet tubes
4 41 discharging of waste liquid of factory service end/recovery pipe
411 first discharging of waste liquid pipes
412 second discharging of waste liquid pipes
413 the 3rd waste liquid delivery pipes
414 the 4th discharging of waste liquid pipes
415 devil liquor recovery pipes
5 air supplies, 51 air delivery pipe
52 pH-value adjustment tanks
6 deployment units
61 chemical raw material groove, 611 medicament delivery pipe
61a bottom discharges end
62 pH-value adjustment tank, 621 pharmaceutical supply pipe
62a top entries end
62b bottom discharges end
62c top entries end
62d top entries end
7 water service source, 71 running water delivery pipe
X1, X2 ramification point
Specific embodiment
The field used due to scarce resources such as dissipated metal, noble metal and rare earth metals is across photoelectricity, ring
The purposes such as guarantor, amusement, national defence, medical treatment, however it is all it has been found that rare earth metal and noble metal at present
May will exhaust after 20 years to 30 years, and prior art is for rare earth gold contained in sci-tech product
The rate of recovery such as category and noble metal is low, often less than 1%；Therefore, content disclosed in this invention is mainly
Can be from semiconductor related process, printed circuit board (PCB) processing procedure, liquid crystal display processing procedure, passive electrical with regard to one kind
The new technology of valuable metal is reclaimed in discarded object produced by subcomponent processing procedure etc. comprehensively, so as to by discarded object
Resource, reaches the purpose of metals resources recycling.
Several preferred embodiments cited below particularly, and coordinate appended accompanying drawing to illustrate embodiments of the present invention,
Those skilled in the art can understand advantages of the present invention and effect by content disclosed in the present specification.In addition,
The present invention can be implemented or be applied by other different specific embodiments, that is to say, that in this specification
Every details also can based on different viewpoints with application, the present invention spirit under carry out it is various modification with become
More.Additionally, appended accompanying drawing not according to the description of actual size, is first given and being chatted only as simple illustrative purposes
It is bright.
(first embodiment)
Fig. 1 is referred to, is that the solid metallic that reclaims from the waste liquid containing metal of first embodiment of the invention is
The block diagram of system.As illustrated, system S of the present embodiment mainly includes a waste liquid temporary storage location 1,
Extraction cells 2 and an electrolysis cells 3, and waste liquid temporary storage location 1, extraction cells 2 and electrolysis cells 3
It is connected with each other between three；From the point of view of functionally, waste liquid temporary storage location 1 is used to keep in a waste liquid containing metal,
Extraction cells 2 are for contained metal ingredient in waste liquid is extracted and back extraction so as to formed legibility from
Metallic compound, electrolysis cells 3 are for being directly reduced to solid-state by the metal ingredient in waste liquid containing metal
Metal, or metallic compound is dissociated and separates out to obtain solid metallic.
First it should be noted that system S of the present embodiment is suitable to process all kinds of processing procedure waste liquids, citing comes
Say, pending processing procedure waste liquid can include noble metal waste liquid, tin-lead soldering waste liquid, acidic etching waste liquid, alkali
Property etching waste liquor, micro-etched waste liquid, electroplating effluent etc. are containing waste liquid more than single metal or bimetallic composition；
And the processing procedure metal ions in waste liquor content after processing is very low, meet the discharge of wastewater mark of legally defined
It is accurate.
In the present embodiment, waste liquid temporary storage location 1 is a waste liquid temporary tank, and extraction cells 2 are included each other
A connected extraction equipment 21 and a back extraction device 22, wherein extraction equipment 21 are a resin tower, instead
Extraction equipment 22 is an extraction tank, and electrolysis cells 3 are an electrolytic cell；It is and preferably designing is, above-mentioned
Waste liquid temporary tank, resin tower, the main body of extraction tank and electrolytic cell be corrosion-resistant material (such as：Stainless steel
Or corrosion-resistant macromolecular material).
An at least concentration detector 11 can be provided with waste liquid temporary storage location 1, for detecting contained gold in waste liquid
The concentration of category composition；By taking metal etch waste liquid as an example, wherein usually containing substantial amounts of copper ion and a small amount of
Other metal ions are (such as：Lead, zinc, aluminium etc.), now can be in the appropriate position in waste liquid temporary storage location 1
Install multiple metal analysis instrument for being respectively directed to the metal ingredients such as copper, lead, zinc and aluminium.
Include the resin for adsorbing metal ions in extraction equipment 21, which can adopt chelating resin, for example
But it is not limited to：Diglycinee type chelating resin () and polyamide chelating resin
()；It will be understood by those skilled in the art that the resin for being configured at extraction equipment 21 can root
Enter line replacement according to metal ingredient contained in pending waste liquid.Subsidiary one carries, and CR11 utilizes two vinegar of imido
Catching metal ion, CR11 has very high selectivity to acid functional group's integration to divalent ion, special
Be not transition metal seem copper, iron etc.；CR20 catches gold using polymeric amine functional group integration
Category ion, CR20 heavy metal ions have high selectivity.
Fig. 2 is referred to, is that the solid metallic that reclaims from the waste liquid containing metal of first embodiment of the invention is
The Organization Chart of system.It is further noted that, waste liquid temporary storage location 1, extraction cells 2 are single with electrolysis
The pipeline of particular design is passed through between unit 3, conveying, circulating reflux and the discharge of waste liquid is capable of achieving.First
Illustrate the connection relationship between waste liquid temporary storage location 1 and extraction cells 2, a top of waste liquid temporary storage location 1
Portion's discharge end 1a is via a liquid delivery tube (not indicating in figure) and a top entry of extraction equipment 21
End 21a is interconnected.Accordingly, when waste liquid containing metal be accumulate in waste liquid temporary storage location 1 it is a certain amount of or
After the concentration of contained metal ingredient in waste liquid is accumulate to a certain amount of, waste liquid containing metal just can be sent to extraction
Device 21 carries out the absorption of metal ion, and reduces the content of the metal ion in waste liquid.
Extraction equipment 21 is simultaneously interconnected via a strip liquor circulation line 23 and back extraction device 22, instead
Extraction liquid circulation line 23 includes a first direction delivery pipe 231 and a second direction delivery pipe 232, wherein
One top discharge end 21b of extraction equipment 21 is via first direction delivery pipe 231 and back extraction device 22
A top entry end 22a be interconnected, and a bottom inlet end 21c of extraction equipment 21 is via second
Direction delivery pipe 232 is interconnected with a bottom discharge end 22b of back extraction device 22.Accordingly, back extraction
Liquid can between extraction equipment 21 and back extraction device 22 circulating reflux repeatedly, and with extraction equipment 21
Collected metal ion is contacted, and a rich metal extraction is formed in making metal ion be transferred to strip liquor
Take liquid.
Next waste liquid temporary storage location 1 and the connection relationship between extraction cells 2 and electrolysis cells 3 are illustrated,
Strip liquor circulation line 23 is further mutually interconnected via an electrolysis cells entrance pipe 31 and electrolysis cells 3
Logical, waste liquid temporary storage location 1 is also interconnected with electrolysis cells 3 via electrolysis cells entrance pipe 31；Tool
Say, electrolysis cells entrance pipe 31 includes a delivery pipe 311 of waste liquid containing metal, a strip liquor discharge body
One bottom discharge end 1b Jing of pipe 312 and an electrolysis cells inlet tube 313, wherein waste liquid temporary storage location 1
One end of electrolysis cells inlet tube 313 is connected by the delivery pipe of waste liquid containing metal 311, and electrolysis cells entrance
The other end of pipe 313 is connected to a top entry end 3a of electrolysis cells 3, and strip liquor delivery pipe 312
It is arranged between ramification point X1 of second direction delivery pipe 232 and electrolysis cells inlet tube 313.Accordingly,
System S can according to contained by pending waste liquid the concentration level of metal ingredient and select to contain metal waste liquid
Or rich metal extraction liquid delivers to electrolysis cells 3, and cell reaction is passed through by reducing metal ions into metal.
Further what deserves to be explained is, the Disposal Measures of water prevention and cure of pollution are integrated with system S, also
It is waste liquid temporary storage location 1, extraction cells 2 can be via one discharging of waste liquid/recovery pipe 41 with electrolysis cells 3
Connect a factory service end 4.Specifically, discharging of waste liquid/recovery pipe 41 includes one first discharging of waste liquid pipe
411st, one second discharging of waste liquid pipe 412, one the 3rd waste liquid delivery pipe 413 and at least one the 4th discharging of waste liquid
Another bottom discharge end 1c of pipe 414, wherein waste liquid temporary storage location 1 is directly via the first discharging of waste liquid pipe
411 connection factory service ends 4, the second discharging of waste liquid pipe 412 are arranged in a point of the delivery pipe of waste liquid containing metal 311
Between bifurcation point X2 and the first discharging of waste liquid pipe 411, another bottom discharge end 22c of back extraction device 22
Second discharging of waste liquid pipe 412 and the first discharging of waste liquid pipe are connected sequentially via the 3rd waste liquid delivery pipe 413
411, and at least discharge end 3b of electrolysis cells 3 connected via at least one the 4th discharging of waste liquid pipe 414
First discharging of waste liquid pipe 411.Accordingly, the waste liquid Jing after extraction, back extraction or electrolysis are processed directly can be arranged
Put to factory service end 4 and processed immediately.
Referring to Fig. 2, system S also includes an air supplies 5, and which is via an air delivery pipe
One air input 3c of 61 connection electrolysis cells 3.Accordingly, when waste liquid containing metal or rich metal extract in electricity
When carrying out cell reaction in solution unit 3, air supplies 5 are sustainable to fitting inside electrolysis cells 3
Work as aeration, with accelerated oxidation reduction efficiency and speed；By taking copper as an example, appropriate aeration can accelerate copper to high price
The transformation of copper.
To implement the Automated condtrol of conveying, circulating reflux and the discharge of waste liquid, strip liquor circulation pipe
Pump and valve member are equipped with road 23, electrolysis cells entrance pipe 31 and discharging of waste liquid/recovery pipe 41
(not indicating in figure), the pump can be high-pressure pump, and the valve member can be liquid valve (chemical valve),
But not limited to this.Accordingly, all valve members can be distinguished with pump by a control unit (not illustrating in figure)
It is controlled by, to adjust the direction of the flow of waste liquid and control waste liquid.
It should be noted that, although in system S shown in Fig. 2, the quantity only one of which of extraction cells 2,
But for the other embodiment of the present embodiment, the quantity of the extraction cells 2 included by system S can be with
It is two or more than three.So, the quantity of the extraction cells 2 shown in Fig. 2 only supplies to illustrate, and
The present invention is not limited.
(second embodiment)
Fig. 3 is referred to, is that the solid metallic that reclaims from the waste liquid containing metal of second embodiment of the invention is
The block diagram of system.As illustrated, compared with previous embodiment, system S ' also include a deployment unit 6,
Which is connected with the back extraction device 22 and electrolysis cells 3 of extraction cells 2 simultaneously, for reclaiming electrolysis cells
3 strip liquors Jing after electrolysis discharged, and supply new strip liquor to back extraction device 22.Remove
This outer, air input of the air supplies 5 via the connection electrolysis cells 3 of an air delivery pipe 51
The one air input 62e of end 3c and pH-value adjustment tank 62, air supplies 5 can be same in this way
When to carrying out aeration inside electrolysis cells 3 and inside pH-value adjustment tank 62.
Fig. 4 is referred to, is that the solid metallic that reclaims from the waste liquid containing metal of second embodiment of the invention is
The Organization Chart of system.Specifically, in the design in configuration with supplying chemical raw material, deployment unit 6 includes
One bottom discharge end of one chemical raw material groove 61 and a pH-value adjustment tank 62, wherein chemical raw material groove 61
61a connects a top entry end 62a of pH-value adjustment tank 62, and acid via a medicament delivery pipe 611
One bottom discharge end 62b of base number adjustment tank 62 connects back extraction device via a pharmaceutical supply pipe 612
22 another top entry end 22d.In the design of Recycling of waste liquid, discharging of waste liquid/recovery pipe 41 is also
Including a devil liquor recovery pipe 615, and at least discharge end 3b of electrolysis cells 3 is via devil liquor recovery pipe 615
Another top entry end 62c of connection pH-value adjustment tank 62.
System S ' also include a water service source 7, which is via the originally connection of transfer pipeline 71 soda acid
The another top entry end 62d of value adjustment tank 62.Accordingly, water service source 7 can be supplied according to process requirement
Appropriate running water is answered to pH-value adjustment tank 62, to adjust the pH value of new strip liquor.Must say
Bright, new strip liquor mentioned herein is by a part of system S ' acid pickle that reclaimed with it is another
Part from after the mixing of original chemical agent adds running water and adjusts its pH value institute former.
The present invention reclaims feature, advantage and the institute of system S (S ') of solid metallic from waste liquid containing metal
The effect that can be reached has been illustrated as above, next will be further described using present system S (S ')
From waste liquid containing metal reclaim solid metallic method.
Fig. 5 is referred to, is a kind of enforcement of the method that solid metallic is reclaimed from waste liquid containing metal of the present invention
The schematic flow sheet of mode.As illustrated, a kind of embodiment of the method at least includes：Step S100,
One waste liquid containing metal is extracted, to isolate the metal ion in waste liquid containing metal；Step S102,
Contacted with metal ion using a strip liquor, one is formed in making metal ion be transferred to strip liquor rich
Metal extraction liquid；And step S104, rich metal extraction liquid is electrolysed, to obtain a solid metallic.
Please refer to Fig. 2 and Fig. 4, in step S100, waste liquid containing metal is in waste liquid temporary storage location 1
Be accumulate to it is a certain amount of after deliver to extraction equipment 21 and extracted, wherein extraction equipment 21 can utilize high score
Sub- polymer is (such as：Chelating resin) catching/adsorbing metal ions.In step S102, back extraction dress
Put 22 and strip liquor can be provided, by taking watery hydrochloric acid as an example, watery hydrochloric acid can be by metal ingredients such as copper, cobalt, zinc, manganese
Back extraction；And strip liquor can via the first and second direction delivery pipes 231,232 in extraction equipment 21 with
Between back extraction device 22 circulating reflux repeatedly, during strip liquor can be by collected by extraction equipment 21
Metal ion is separated out, and rich metal extraction liquid is formed in making metal ion be sunken to strip liquor.Step S104
In, rich metal extraction liquid can sequentially flow through strip liquor delivery pipe 312 and electrolysis cells inlet tube 313 and lead to
Enter in electrolysis cells 3, and metallic compound therein dissociates through cell reaction and separate out to obtain
Solid metallic.
Fig. 6 is referred to, is that the method that solid metallic is reclaimed from waste liquid containing metal of the present invention is another kind of real
Apply the schematic flow sheet of mode.As illustrated, the another embodiment of the method at least includes：Step
S200, a waste liquid containing metal is imported and is kept in a waste liquid temporary storage location；Step S202, detection contain
The concentration of contained metal ingredient in metal waste liquid；Step S204, will contain metal waste liquid according to testing result and enter
Row electrolysis, by the reducing metal ions of the rather high concentration in waste liquid containing metal into a solid metallic；
Step S206, the waste liquid containing metal Jing after being electrolysed is sent back in waste liquid temporary storage location and is kept in.
Please refer to Fig. 2 and Fig. 4, in step S200 and step S202, waste liquid containing metal can be from setting
Prepare Cheng Duan (not shown) to import in waste liquid temporary storage location 1, when waste liquid containing metal is accumulate to necessarily
The concentration of metal ingredient contained by which is detected during amount using an at least concentration detector 11；In step S204,
If testing result shows that contained a certain metal ingredient is (such as in waste liquid containing metal：Copper ion) concentration be more than
One specific numerical value is (such as：5wt% ± 0.5wt%) when, waste liquid containing metal can sequentially flow through waste liquid containing metal
Delivery pipe 311 and electrolysis cells inlet tube 313 and be passed in electrolysis cells 3, and pass through cell reaction
By the metallic compound in metal extraction liquid (such as：Copper-based compound) dissociate and separate out to obtain solid-state gold
Category is (such as：Metallic copper)；In step S206, by the waste liquid containing metal Jing after being electrolysed as metal ion contains
Amount it is very low, for example, Jing electrolysis after waste liquid containing metal in may only it is remaining it is micro gold or silver ion, therefore
Can be selected send back to according to process requirement and carry out in waste liquid temporary storage location 1 temporary and accumulate again.
What deserves to be explained is, if testing result shows that the concentration of contained metal ingredient in waste liquid containing metal is less than
During one specific numerical value, system S (S ') can select to carry out above-mentioned step S100 to step S104.With
Illustrate as a example by copper, if contained copper ion concentration is more than 5wt% ± 0.5wt%/gold or concentration of silver ions in waste liquid
During more than 3wt% ± 0.5wt%, system S (S ') can select to perform above-mentioned step S100 to step S104；
If contained copper ion concentration is more than 5wt% ± 0.5wt%/gold or concentration of silver ions is less than 3wt% ± 0.5wt%
When, system S (S ') can select to perform above-mentioned step S200 to step S206.Accordingly, electricity can be extended
The service life of substrate (battery lead plate) and the resin in extraction equipment 21 in solution unit 3, and save use
Electric cost.
Fig. 7 is referred to, is method another reality of recovery solid metallic from waste liquid containing metal of the present invention
Apply the schematic flow sheet of mode.As illustrated, another embodiment of the method at least includes：Step
S300 a, there is provided waste liquid containing metal, this contains metal waste liquid comprising one first metal ion and one second metal
The concentration of ion, the wherein concentration of first metal ion higher than second metal ion；Step S302,
The waste liquid containing metal is extracted, with second metal ion being previously isolated from out in the waste liquid containing metal；
This Jing after extracting is contained metal waste liquid and is electrolysed, to obtain corresponding to first metal by step S304
One first solid metallic of ion, and while contacted with second metal ion using a strip liquor,
A rich metal extraction liquid is formed in making second metal ion be transferred to the strip liquor；And step
S306, the rich metal extraction liquid is electrolysed, to obtain one second corresponding to second metal ion
Solid metallic.
In step S300, it is containing double to import the waste liquid containing metal in waste liquid temporary storage location 1 from equipment processing procedure end
Waste liquid more than metal ingredient, for example, the gold ion of the copper ion containing high concentration and low concentration in waste liquid；
In step S302, waste liquid containing metal can first be delivered to extraction equipment 21 and be extracted, by copper therein from
Son grabs (copper ion is adsorbed by resin), is so left gold ion in waste liquid containing metal；Step S304
In, waste liquid containing metal then can be sent in electrolysis cells 3, and first obtains metallic gold through cell reaction,
Back extraction device 22 can provide strip liquor, and strip liquor in extraction equipment 21 and back extraction device 22 afterwards
Between circulating reflux repeatedly, copper ion of the absorption on resin is separated out, makes copper ion be sunken to strip liquor
In and formed copper-rich extract；In step S306, copper-rich extract can be sent in electrolysis cells 3 again,
And also pass through cell reaction and first obtain metallic copper.In this way, the method for the present invention is also adapted to containing double gold
Waste liquid more than category composition.Subsidiary one carries, and the quantity of extraction cells 2 can be based on institute in pending waste liquid
Quantity containing metal ingredient is adjusted；And preferably designing is, the quantity of extraction cells 2 is equal to metal
The quantity of composition adds one, so can significantly increase the organic efficiency of metals resources.
(the possibility effect of embodiment)
In sum, compared to the processing mode of existing metal ion waste liquid, the present invention at least has
Following advantage：
The system of the present invention will be waste liquid temporary storage location, extraction cells and electrolysis single through the pipeline of particular design
Unit is connected with each other together, can according to contained by waste liquid metal ingredient concentration, selection first extracted/
Processing mode that back extraction is then electrolysed or the processing mode for being first electrolysed then extraction/back extraction, therefore not only
Can greatly improve the rate of recovery of metal, but also the substrate (battery lead plate) that can extend in electrolysis cells and extraction
The service life of the resin in device is taken, the purpose that effect saves consumables cost and electric cost is reached.
Furthermore, the present invention system through deployment unit configuration, can by the acid pickle of recovery with never make
Running water is added after used chemical agent mixing and adjusts its pH value, meet recycling back extraction to be formed
The secondary strip liquor of the standard of liquid, therefore can further save the cost of strip liquor.
In addition, can be from semiconductor related process, printing electricity using the processing method of the system of the present invention
Returned in discarded object produced by road plate processing procedure, liquid crystal display processing procedure, passive electronic components processing procedure etc. comprehensively
Valuable metal is received, and the metal purity for being reclaimed is high and recycling property is good.And in the processing procedure waste liquid after processing
Metal ion content is very low, meets the wastewater discharge standard of legally defined.
Presently preferred embodiments of the present invention is only the foregoing is only, is not intended to limit to the patent protection model of the present invention
Enclose, therefore be all contained in the same manner with the equivalence changes carried out by description of the invention and accompanying drawing content such as
In the scope of the present invention, Chen Ming is given in conjunction.
Claims (17)
1. a kind of system that solid metallic is reclaimed from waste liquid containing metal, it is characterised in that should be from containing metal
The system that solid metallic is reclaimed in waste liquid includes：
One waste liquid temporary storage location, for keeping in a waste liquid containing metal；
One extraction cells, the extraction cells are connected with the waste liquid temporary storage location, and the extraction cells include an extraction
Device and a back extraction device, the wherein extraction equipment be used to collecting a metal in the waste liquid containing metal from
Son, the back extraction device for by the metal ion back extraction collected by the extraction equipment into a strip liquor
And form a metallic compound；And
One electrolysis cells, the electrolysis cells are connected with the extraction cells, for by the waste liquid containing metal should
Metal ion is directly reduced to a solid metallic, or the metallic compound in the strip liquor is dissociated and separated out
To obtain the solid metallic.
2. the system for reclaiming solid metallic as claimed in claim 1 from waste liquid containing metal, the wherein extraction
Take device to be interconnected with the back extraction device via a strip liquor circulation line, the strip liquor circulation line enters
One step is interconnected via an electrolysis cells entrance pipe and the electrolysis cells, the waste liquid temporary storage location also via
The electrolysis cells entrance pipe is interconnected with the electrolysis cells.
3. the as claimed in claim 2 system that solid metallic is reclaimed from waste liquid containing metal, wherein this is useless
One top discharge end of liquid temporary storage location is interconnected with a top entry end of the extraction equipment, the strip liquor
Circulation line includes a first direction delivery pipe and a second direction delivery pipe, and at the top of the one of the extraction equipment
A top entry end of the discharge end via the first direction delivery pipe with the back extraction device is interconnected, and should
Arrange a bottom of the one bottom inlet end of extraction equipment via the second direction delivery pipe with the back extraction device
Put end to be interconnected.
4. the system for reclaiming solid metallic as claimed in claim 3 from waste liquid containing metal, the wherein electricity
Solution unit entrance pipe includes a delivery pipe of waste liquid containing metal, a strip liquor delivery pipe and an electrolysis cells entrance
Pipe, a bottom discharge end of the waste liquid temporary storage location connects the electrolysis cells via the delivery pipe of waste liquid containing metal
One end of inlet tube, and the other end of the electrolysis cells inlet tube is connected to a top entry of the electrolysis cells
End, and the strip liquor delivery pipe is arranged in a ramification point and the electrolysis cells entrance of the second direction delivery pipe
Between pipe.
5. the as claimed in claim 1 system that solid metallic is reclaimed from waste liquid containing metal, wherein this is useless
Liquid temporary storage location, the extraction equipment and the electrolysis cells connect a factory via one discharging of waste liquid/recovery pipe
Business end.
6. the as claimed in claim 5 system that solid metallic is reclaimed from waste liquid containing metal, wherein this is useless
Liquid discharge/recovery pipe includes one first discharging of waste liquid pipe, one second discharging of waste liquid pipe, one the 3rd waste liquid row
Put pipe and at least one the 4th discharging of waste liquid pipe, another bottom discharge end of the waste liquid temporary storage location via this first
Discharging of waste liquid pipe connects the factory service end, and the second discharging of waste liquid pipe is arranged in the one of the delivery pipe of waste liquid containing metal
Between ramification point and the first discharging of waste liquid pipe, another bottom discharge end of the back extraction device is via the 3rd
Discharging of waste liquid pipe sequentially connects the second discharging of waste liquid pipe and the first discharging of waste liquid pipe, and the electrolysis cells
An at least discharge end connects the first discharging of waste liquid pipe via at least one the 4th discharging of waste liquid pipe.
7. the system that solid metallic is reclaimed from waste liquid containing metal as claimed in claim 1, further includes one
Deployment unit, the deployment unit are connected with the back extraction device and the electrolysis cells, for reclaiming the electrolysis list
Strip liquor Jing after electrolysis that unit is discharged, and the new strip liquor is supplied to the back extraction device.
8. the system for reclaiming solid metallic as claimed in claim 7 from waste liquid containing metal, the wherein tune
Include a chemical raw material groove and a pH-value adjustment tank, a bottom discharge end Jing of the chemical raw material groove with unit
One top entry end of the pH-value adjustment tank, and the one of the pH-value adjustment tank are connected by a medicament delivery pipe
Bottom discharge end connects another top entry end of the back extraction device via a pharmaceutical supply pipe.
9. the as claimed in claim 8 system that solid metallic is reclaimed from waste liquid containing metal, wherein this is useless
Liquid discharge/recovery pipe further includes a devil liquor recovery pipe, and a discharge end of the electrolysis cells is returned via the waste liquid
Closed tube connects another top entry end of the pH-value adjustment tank.
10. the system that solid metallic is reclaimed from waste liquid containing metal as claimed in claim 9, further includes one
Water service source and an air supplies, the water service source connect the acid via a running water delivery pipe
The another top entry end of base number adjustment tank, the air supplies are connected simultaneously via an air delivery pipe should
One air input of electrolysis cells and an air input of the pH-value adjustment tank.
The 11. as claimed in claim 1 systems that solid metallics are reclaimed from waste liquid containing metal, wherein this is useless
A concentration detector is provided with liquid temporary storage location, for detecting the metal concentration containing metal waste liquid.
A kind of 12. methods that solid metallic is reclaimed from waste liquid containing metal, it is characterised in that should be from containing metal
The method that solid metallic is reclaimed in waste liquid comprises the following steps：
One waste liquid containing metal is extracted, to isolate the metal ion in the waste liquid containing metal；
Contacted with the metal ion using a strip liquor, in making the metal ion be transferred to the strip liquor
Form a rich metal extraction liquid；And
The rich metal extraction liquid is electrolysed, to obtain a solid metallic.
13. methods that solid metallic is reclaimed from waste liquid containing metal as claimed in claim 12, wherein in institute
Before stating the step of extracting a waste liquid containing metal, methods described also includes importing a waste liquid containing metal
Kept in one waste liquid temporary storage location.
14. methods that solid metallic is reclaimed from waste liquid containing metal as claimed in claim 13, wherein in institute
State to import to carry out further including in temporary step in a waste liquid temporary storage location by a waste liquid containing metal and detect that this contains
The metal concentration of metal waste liquid.
15. methods that solid metallic is reclaimed from waste liquid containing metal as claimed in claim 14, wherein in institute
State will a waste liquid containing metal import carry out in a waste liquid temporary storage location temporary step with it is described by one containing metal
Between before the step of waste liquid is extracted, methods described also comprises the following steps：
According to the testing result of the metal concentration containing metal waste liquid, and in advance a high concentration metal waste liquid is entered
Row electrolysis, to reclaim the high concentration metal in the high concentration metal waste liquid；And
The high concentration metal waste liquid Jing after being electrolysed is imported and is kept in the waste liquid temporary storage location.
The methods of the 16. recovery solid metallics from waste liquid containing metal as claimed in claim 12, wherein this is anti-
Extraction liquid is hydrochloric acid.
A kind of 17. methods that solid metallic is reclaimed from waste liquid containing metal, it is characterised in that should be from containing metal
The method that solid metallic is reclaimed in waste liquid comprises the following steps：
One waste liquid containing metal is provided, this contain metal waste liquid include one first metal ion and one second metal from
The concentration of son, the wherein concentration of first metal ion higher than second metal ion；
The waste liquid containing metal is extracted, with second metal that is previously isolated from out in the waste liquid containing metal from
Son；
This Jing after extracting is contained metal waste liquid to be electrolysed, to obtain corresponding to first metal ion
First solid metallic, and while contacted with second metal ion using a strip liquor, make second gold medal
Category ion-transfer forms a rich metal extraction liquid into the strip liquor；And
The rich metal extraction liquid is electrolysed, to obtain one second solid-state corresponding to second metal ion
Metal.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510633876.4A CN106555055A (en) | 2015-09-29 | 2015-09-29 | The system and method for solid metallic is reclaimed from waste liquid containing metal |
| US15/130,541 US20170088964A1 (en) | 2015-09-29 | 2016-04-15 | System and method for recovering metal from metal-containing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510633876.4A CN106555055A (en) | 2015-09-29 | 2015-09-29 | The system and method for solid metallic is reclaimed from waste liquid containing metal |
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| CN106555055A true CN106555055A (en) | 2017-04-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510633876.4A Pending CN106555055A (en) | 2015-09-29 | 2015-09-29 | The system and method for solid metallic is reclaimed from waste liquid containing metal |
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| US (1) | US20170088964A1 (en) |
| CN (1) | CN106555055A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724973A (en) * | 2019-11-19 | 2020-01-24 | 安徽焦冲矿业有限公司 | Efficient environment-friendly high-purity gold preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108716020A (en) * | 2018-05-29 | 2018-10-30 | 南京八度阳光太阳能科技有限公司 | A kind of making herbs into wool waste material recycling device used for solar batteries |
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| CN1154723A (en) * | 1995-05-12 | 1997-07-16 | 株式会社艾恩 | Method for recycling waste etching solution |
| CN101688315A (en) * | 2007-07-11 | 2010-03-31 | 西格玛工程集团 | A method for etching copper and recovery of the spent etching solution |
| CN202595280U (en) * | 2012-03-09 | 2012-12-12 | 广东东日环保有限公司 | Alkaline etching solution recovering device |
| JP5181684B2 (en) * | 2008-01-15 | 2013-04-10 | 住友金属鉱山株式会社 | Solvent extraction method for aqueous chloride solution |
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| CN1154723A (en) * | 1995-05-12 | 1997-07-16 | 株式会社艾恩 | Method for recycling waste etching solution |
| CN101688315A (en) * | 2007-07-11 | 2010-03-31 | 西格玛工程集团 | A method for etching copper and recovery of the spent etching solution |
| JP5181684B2 (en) * | 2008-01-15 | 2013-04-10 | 住友金属鉱山株式会社 | Solvent extraction method for aqueous chloride solution |
| CN202595280U (en) * | 2012-03-09 | 2012-12-12 | 广东东日环保有限公司 | Alkaline etching solution recovering device |
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| CN110724973A (en) * | 2019-11-19 | 2020-01-24 | 安徽焦冲矿业有限公司 | Efficient environment-friendly high-purity gold preparation method |
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