CN109680150B - Method and device for extracting and recovering metal by using electrodialysis in cooperation with microemulsion - Google Patents
Method and device for extracting and recovering metal by using electrodialysis in cooperation with microemulsion Download PDFInfo
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- CN109680150B CN109680150B CN201711013135.1A CN201711013135A CN109680150B CN 109680150 B CN109680150 B CN 109680150B CN 201711013135 A CN201711013135 A CN 201711013135A CN 109680150 B CN109680150 B CN 109680150B
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- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 109
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 62
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 238000005341 cation exchange Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000012071 phase Substances 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 27
- 239000008346 aqueous phase Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- SRFRNRNAHYJZKX-UHFFFAOYSA-M dodecyl sulfate;tetraoctylazanium Chemical class CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SRFRNRNAHYJZKX-UHFFFAOYSA-M 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 3
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 3
- 239000001593 sorbitan monooleate Substances 0.000 claims description 3
- 229950004959 sorbitan oleate Drugs 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 description 27
- 239000010941 cobalt Substances 0.000 description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 27
- 229910052759 nickel Inorganic materials 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000008139 complexing agent Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- -1 nickel metals Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 229920000053 polysorbate 80 Polymers 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a device for extracting and recovering metals by using microemulsion under the coordination of electrodialysis, which comprises a positive electrode tank, a raw material tank, an extraction tank, a collecting tank and a negative electrode tank, wherein the positive electrode tank, the raw material tank, the extraction tank, the collecting tank and the negative electrode tank are sequentially arranged according to the above sequence, and are sequentially and respectively separated from each other by a first anion exchange membrane, a first cation exchange membrane, a second cation exchange membrane and a second anion exchange membrane. The method for recovering valuable metals by using the device comprises the steps of applying voltage to the positive electrode tank and the negative electrode tank, and enabling a plurality of metal ions in the raw material tank to pass through the first cation exchange membrane to reach the extraction tank so as to be combined with the ammonium thiocyanate solution forming the microemulsion in the extraction tank and the oil phase extracting agent respectively, thereby achieving the purpose of purifying the plurality of metal ions.
Description
Technical Field
The invention relates to a method and a device for recovering metals, in particular to a method and a device for extracting and recovering metals by using electrodialysis in cooperation with microemulsion.
Background
Because the prices of cobalt and nickel are continuously rising, the recovery of cobalt and nickel is greatly emphasized, and particularly, the problem of how to improve the recovery purity of cobalt and nickel becomes the most important technology. Because the chemical properties of cobalt and nickel metals are very similar, the co-production or associated phenomena in ore deposits often occur, for example, nickel is often carried in various cobalt waste residues, and also cobalt and nickel are often simultaneously contained in various special alloys, battery materials or catalysts, wherein the demand for cobalt is higher, and the yield is increasingly exhausted, so that the separation of cobalt and nickel and the improvement of purity are very important issues. In the existing separation and purification technology, most of the methods adopt a precipitation method and a solvent extraction method.
In the precipitation method, a solution having a substantially equivalent cobalt-nickel concentration is generated in the recovery of cobalt-nickel metal, particularly in the metal recovery process of a lithium battery, and co-precipitation occurs during the precipitation process, so that complete separation cannot be achieved. In contrast, the solvent extraction method has become a main method for separating cobalt and nickel industrially due to its advantages of high selectivity, high recovery rate, simple process, continuous operation, easy realization of automation, etc.
In the solvent extraction technology, the nickel-cobalt extraction separation technology in the sulfate solution system is mature and widely applied in industry. On the other hand, the chloride system has the characteristics of high nickel-cobalt extraction separation coefficient, capability of back extracting calcium and magnesium by using water, no co-extraction along with cobalt extraction, high metal concentration of chloride solution, small circulating flow in the technical process and the like. However, the method has limitations in that the concentration of chloride ions in the solution is high, the equipment is severely corrosive, and the operation and control are difficult, so compared with the sulfate system, the method for extracting and separating nickel and cobalt by using the chloride system cannot be widely applied.
Therefore, methods for extraction by electrodialysis have been proposed, which can improve the separation efficiency of mixed metals in extraction equipment due to the addition of an electric field and an ion exchange membrane. The electric field used in the extraction process has the main function of adding a direct current electric field between bath solution separated by an ion exchange membrane in an extraction system, so that the ion diffusion rate can be increased, and the separation efficiency of mixed metal is improved.
The typical electrodialysis extraction equipment is U-shaped tube type intermittent electrodialysis extraction equipment, and during experiments, two immiscible oil/water phases are placed at two ends of a U-shaped tube, and positive and negative electrodes are respectively added to the electrodes in the two phases. The other intermittent electrophoretic extraction equipment has microporous membrane to separate the cavity into positive electrode chamber, negative electrode chamber and oil/water separating chamber, and buffering liquid with certain pH value is circulated in the two-phase electrode space to ensure the gradient of pH value in the oil/water separating chamber and avoid great change caused by electrode reaction. However, the metal separation efficiency of both is far lower than that of the traditional solvent extraction procedure, and the mixed metal ions cannot be effectively separated, so that a certain degree of separation effect can be achieved by 6-12 stages of continuous countercurrent extraction.
Therefore, the above prior art cannot actually improve the purity of the recovered metal, and the process is complicated and time-consuming, and cannot be separated efficiently. In view of the above, the inventor of the present invention has studied, thought and designed a method and a device for recovering metals by microemulsion extraction in cooperation with electrodialysis, so as to improve the defects of the prior art and further enhance the industrial application.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to an extraction method and apparatus for efficiently separating a plurality of metal ions from a solution, and to an industrial mass separation method and apparatus therefor.
In view of the above, the present invention provides an apparatus for recovering metals by electrodialysis in cooperation with microemulsion extraction, which comprises a positive electrode tank, a raw material tank, an extraction tank, a collection tank, and a negative electrode tank. The positive electrode groove is used for containing electrode liquid; a raw material tank for containing an aqueous phase solution containing a first metal ion and a second metal ion; an extraction tank for containing ammonium thiocyanate (NH)4SCN) solution, cetyl trimethyl ammonium bromide (CTMAB) and an oil phase extracting agent, wherein the binding force of the oil phase extracting agent to the first metal ions is less than that of the ammonium thiocyanate solution to the first metal ions; a collecting tank for containing an electrolyte solution in which the second metal ions are soluble; the negative electrode tank is used for containing electrode liquid and communicated with the positive electrode tank to provide potential difference; the tanks are respectively arranged according to the sequence of the anode tank, the raw material tank, the extraction tank, the collecting tank and the cathode tank, and are respectively separated from one another by a first anion exchange membrane, a first cation exchange membrane, a second cation exchange membrane and a second anion exchange membrane in sequence.
Preferably, the electrolyte solution has the same anion as the aqueous solution.
Preferably, the microemulsion further comprises a surfactant for assisting oil-water mixing of the microemulsion.
Preferably, the surfactant comprises polyoxyethylene sorbitan oleate (Tween80), sorbitan monooleate (Span80), quaternary ammonium salts of tetraoctylammonium lauryl sulfate, or any combination thereof.
Preferably, the extraction tank is connected with the extraction liquid circulation tank so as to maintain the oil-water mixing state of the microemulsion in the extraction tank by a circulating stirring mode.
Preferably, the electrolyte comprises a solution of the same sodium or potassium salt as the anion of said aqueous solution.
In view of the above object, the present invention further provides a method for metal recovery using the above apparatus for recovering metals by electrodialysis in cooperation with microemulsion extraction, comprising: providing said potential difference to said anode cell and said cathode cell at a first predetermined time to perform an extraction procedure, said potential difference causing said first metal ion and said second metal ion to become localized in said extraction cell after passing from said feed cell through said first cation exchange membrane, wherein said first metal ion binds to an ammonium thiocyanate solution in said microemulsion and said second metal ion binds to an oil phase extractant in said microemulsion.
Preferably, the first predetermined time may be a time at which a separation rate of the first metal ion and the second metal ion in the microemulsion is maximized.
Preferably, the method of the present invention further comprises standing the extraction tank until the ammonium thiocyanate solution (aqueous phase) and the oil phase extractant (oil phase) are separated from each other after the extraction procedure is completed, and then performing back extraction after the ammonium thiocyanate solution and the oil phase extractant are respectively taken out to obtain the first metal ions and the second metal ions.
Preferably, the method of the present invention further comprises, after the extraction procedure is completed, draining the liquid from the feed tank and the holding tank, introducing a first acid solution into the feed tank, and introducing a second acid solution having a concentration less than that of the first acid solution into the holding tank; and providing a potential difference to the anode tank and the cathode tank at a second predetermined time to allow second metal ions in the oil phase extractant to pass through the second cation exchange membrane to enter the collection tank, wherein the first acid solution and the second acid solution have the same anion as the aqueous phase solution.
As mentioned above, the method and apparatus for recovering metals by electrodialysis in cooperation with microemulsion extraction according to the present invention can have one or more of the following advantages:
(1) the electrodialysis cooperated with the microemulsion extraction device has the advantages that the ion membrane is used for isolating the aqueous phase solution, the oil phase extraction liquid and the low-salt water solution, the loss of high-value solvent in the conductive extraction liquid in the extraction process is avoided, the process is carried out in the closed membrane group, and the pollution to the operating environment is low.
(2) The invention uses water phase complexing agent ammonium thiocyanate (NH)4SCN) and an oil phase extractant (P507) can simultaneously and respectively complex and extract two metals with similar chemical properties, and the separation purity is about 1000:1 when the extraction liquid is used for separating cobalt (Co) and nickel (Ni), namely the purity of 99.9 percent can be achieved by one stage without multistage continuous countercurrent extraction.
(3) The present invention can adopt the existing cation exchange membrane and anion exchange membrane in the market, and has lower cost and practicability for the grooving or the mass production through the proper dialysis membrane group design and the optimal parameter operation.
(4) Compared with other traditional solvent extraction technologies, the method can avoid a large amount of acid and alkali resources and cost consumed in the processes of cyclic extraction and back extraction, and reduce environmental pollution. In addition, the invention directly operates in water phase, the separated metal complex anion is directly collected in the extraction tank and regenerated by weak base, and the complexing agent can be recycled, thus having the effects of reducing cost and pollution.
Drawings
FIG. 1 is a schematic diagram of an extraction system for the extraction recovery of metals from microemulsions in conjunction with electrodialysis, in accordance with the present invention.
Fig. 2 is a diagram of the steps of a method according to the invention.
Fig. 3 is a diagram of another step of the method according to the invention.
FIG. 4 is a graph showing the variation of the cobalt and nickel contents in the aqueous phase complexing agent according to the embodiment of the present invention.
FIG. 5 is a graph showing the variation of cobalt and nickel contents in the oil phase extractant in accordance with one embodiment of the present invention.
Description of the symbols:
10: positive electrode groove, 11: negative electrode groove, 12: electrode solution, 13: electrode liquid tank external circulation tank, 20: raw material tank, 21: aqueous phase solution, 22: aqueous phase supply tank, 30: extraction tank, 31: microemulsion, 34: extract liquid circulation tank, 40: a collecting tank, 41: electrolyte solution, 42: collection tank external circulation tank, 51: first anion exchange membrane, 52: first cation exchange membrane, 53: second cation exchange membrane, 54: second anion exchange membrane, S10-S40: and (5) carrying out the following steps.
Detailed Description
In order to make the above objects, technical features and gains obvious and understandable after practical implementation, preferred embodiments will be described in detail below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of an extraction system for the extraction recovery of metals from microemulsions in conjunction with electrodialysis, in accordance with the present invention. As shown in the figure, the extraction system comprises an electrodialysis cooperating with microemulsion extraction and metal recovery device, which comprises a positive electrode tank 10, a negative electrode tank 11, a raw material tank 20, an extraction tank 30, a first anion exchange membrane 51, a first cation exchange membrane 52, a second cation exchange membrane 53 and a second anion exchange membrane 54. The above-described arrangement of the respective tanks and the ion exchange membranes is such that the positive electrode tank 10, the raw material tank 20, the extraction tank 30, the collection tank 40, and the negative electrode tank 11 are arranged in order, and are separated from one another in order by the first anion exchange membrane 51, the first cation exchange membrane 52, the second cation exchange membrane 53, and the second anion exchange membrane 54, respectively.
The positive electrode tank 10 and the negative electrode tank 11 are provided with electrodes, and can provide potential difference to the device for extracting and recovering metals by cooperating with the microemulsion when the system is electrified, the spaces in the positive electrode tank 10 and the negative electrode tank 11 are used for containing electrode liquid 12, and the positive electrode tank 10 and the negative electrode tank 11 can be communicated through pipelines, so that the electrode liquid 12 can be circulated.
The raw material tank 20 is configured to accommodate an aqueous solution 21, where the aqueous solution 21 contains a first metal ion and a second metal ion to be recovered.
The extraction tank 30 is configured to accommodate a microemulsion 31, where the microemulsion 31 includes an ammonium thiocyanate solution, cetyltrimethyl ammonium bromide (CTMAB), and an oil phase extraction agent, where the oil phase extraction agent is an extraction solvent in the known extraction technology, and the extraction solvent may be used, where the binding force of the extraction solvent to the first metal ions is smaller than that of the ammonium thiocyanate solution. The CTMAB is mixed in the microemulsion 31 for the purpose of prolonging the time for maintaining the oil-water mixing state after the microemulsion 31 is stirred, so that the stirred microemulsion 31 can maintain the mixing state only by a circulating stirring mode, and the conductivity of the liquid in the extraction tank 30 is kept.
The holding tank 40 may be used to contain an electrolyte solution 41, such as a sulfuric acid solution, in which the second metal ions may be dissolved.
The electrode liquid tank external circulation tank 13, the water phase supply tank 22, the extract liquid circulation tank 34 and the collecting tank external circulation tank 42 can be added into the above tanks to form an extraction system for extracting and recovering metals by using the microemulsion liquid in cooperation with electrodialysis.
The electrode liquid tank external circulation tank 13 is used for communicating the positive electrode tank 10 and the negative electrode tank 11, so that the electrode liquid 12 can be circulated to balance the charge of the whole purification system. The electrode liquid 12 may comprise a solution of a sodium or potassium salt of the same anion as the aqueous solution 21. The aqueous phase supply tank 22 may feed the aqueous phase solution 21 to be separated into the raw material tank 20; the extraction liquid circulating tank 34 can convey the microemulsion 31 to the extraction tank 30 and stir the microemulsion 31 through circulation of liquid; the tank external circulation tank 42 may supply the electrolyte solution 41 to the tank 40, or recover the electrolyte solution 41 already containing the second metal ions.
In practice, a surfactant, such as polyoxyethylene sorbitan oleate (Tween80), sorbitan monooleate (Span80), quaternary ammonium salt of tetraoctylammonium dodecyl sulfate, etc., may be added to further assist the oil-water mixing of the microemulsion 31, so as to realize the electrodialysis process, avoid the influence of the rapid phase separation of the microemulsion 31 on the conductivity, and avoid the continuous physical stirring.
In practice, the above-described aqueous phase supply tank 22 may be provided for circulating the aqueous phase solution 21 outside the raw material tank 20 during the extraction process, and the collection tank external circulation tank 42 may be provided for circulating the electrolyte solution 41 outside the collection tank 40 during the extraction process.
Referring to fig. 1 and fig. 2, fig. 2 is a flowchart illustrating a method according to the present invention, which includes the following steps:
step S10: an apparatus for recovering metals by electrodialysis in conjunction with microemulsion extraction was provided, the apparatus being constructed as described above.
Step S20: a potential difference is applied to the positive electrode tank 10 and the negative electrode tank 11 at a first predetermined time to perform an extraction process. At this time, the first metal ions and the second metal ions are drawn through the first cation exchange membrane 52 into the extraction tank 30 by the electric field. Furthermore, because the microemulsion 31 in the extraction tank 30 contains both the aqueous phase complexing agent ammonium thiocyanate solution and the oil phase extractant, and the binding force of the oil phase extractant to the first metal ions is smaller than that of the ammonium thiocyanate solution, the first metal ions are bound with the ammonium thiocyanate solution, and the second metal ions are bound with the oil phase extractant.
In this way, the first metal ions and the second metal ions are confined in the microemulsion 31 of the extraction tank 30, and since the first metal ions and the second metal ions are respectively combined with the ammonium thiocyanate solution and the oil phase extractant, the purpose of separating the first metal ions and the second metal ions in the aqueous phase solution 21 can be achieved.
The method for recovering metals by electrodialysis in conjunction with microemulsion extraction according to the present invention can also be selectively performed in the following step S30 or step S40 depending on the degree of purification and separation.
In step S30, after the extraction process of step S20 is completed, the ammonium thiocyanate solution (aqueous phase) and the oil phase extractant (oil phase) are allowed to stand until the ammonium thiocyanate solution (aqueous phase) and the oil phase extractant (oil phase) in the extraction tank 30 are separated from each other, and the ammonium thiocyanate solution and the oil phase extractant are taken out separately and subjected to back extraction to obtain the first metal ions and the second metal ions. Since the extraction procedure of step S20 can achieve a purity of about 99.9% by only one-stage extraction, the high-purity metal can be obtained by directly back-extracting the extracted ammonium thiocyanate solution and the oil phase extractant.
The back extraction can be carried out in a conventional manner, for example, for the oil phase extractant, sulfuric acid can be added into the oil phase extractant, and the mixture is stirred, mixed and clarified to enable the sulfuric acid and metal ions in the oil phase extractant to form a sulfate solution. For the aqueous phase complexing agent (ammonium thiocyanate solution), the oil phase extractant may be stirred, mixed and clarified at a suitable pH (e.g., 4.5) to extract the metal ions in the aqueous phase complexing agent into the oil phase, and then the sulfate solution may be obtained in the same manner as described above for the oil phase extractant. Since the stripping can be completed within several minutes, the time required for recovering the metal can be greatly reduced, and the recovery efficiency can be improved.
On the other hand, if the recovered metal is to be further purified, stripping may be performed in step S40 instead of step S30. As shown in fig. 3, in step S40, after the extraction process of step S20 is completed, the liquids in the raw material tank 20 and the collection tank 40 are drained, the first acid solution is introduced into the raw material tank 20, and after the second acid solution with a concentration lower than that of the first acid solution is introduced into the collection tank 40, the electric dialysis is performed again by applying a potential difference to the positive electrode tank 10 and the negative electrode tank 11 for a second predetermined time. At this time, the second metal ions (positive ions) combined with the oil phase extractant in the extraction tank 30 are replaced and dissociated by the high concentration hydrogen ions passing through the first cation exchange membrane 52 from the raw material tank 20, and pass through the second cation exchange membrane 53 to the collection tank 40. On the other hand, the complex ions (negative ions) of the first metal combined with the ammonium thiocyanate solution in the extraction tank 30 are confined in the extraction tank 30 by the first cation exchange membrane 52 and the second cation exchange membrane 53 on both sides, so that the first metal ions and the second metal ions can be further separated and purified. In addition, the first acid solution and the second acid solution herein may have the same anion as the aqueous phase solution 21 in the raw material tank 20, and the anion concentration in the first acid solution introduced into the raw material tank 20 may be higher than the aqueous phase solution 21 originally having metal ions.
The electrodialysis method of step S40 takes more time and material costs than the method of step S30, but since the purity of the extracted metal is higher than that of the method of step S30, it is preferable to increase the recovery rate of the metal as much as possible when the method is used for separating and purifying the expensive metal.
The following is a test for recovering a metal material using the apparatus for recovering a metal by electrodialysis in cooperation with microemulsion extraction of the present invention.
In this example, the aqueous solution in the raw material tank 20 contained 0.5g each of cobalt (Co) powder and nickel (Ni) powder, and 400mL of a 2% sulfuric acid solution.
The microemulsion in the extraction tank 30 contained 300mL of 1M ammonium thiocyanate solution, 100mL of 0.1M CTMAB, 70mL of kerosene, and 30mL of saponified 70% P507(2-ethylhexyl 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate) in a total of 500mL, and 50mL of Tween80 was added to keep the aqueous and oil phases from separating for about 3 hours. Wherein, P507 which is saponified by 70 percent is not conductive per se, and is mixed with the ammonium thiocyanate solution and the surfactant CTMAB and Tween80 to form microemulsion which has the conductive property.
The electrolyte solution in the holding tank 40 was 400mL of a 0.4% sulfuric acid solution. The electrode solution in the positive electrode tank 10 and the negative electrode tank 11 was 400mL of a 1% sodium sulfate solution.
The volume of each tank was 400mL, the excess microemulsion was used for the circulation outside the extraction tank 30, a constant voltage of 30V and a constant current of 130mA were applied for 24 hours during the experiment, samples were taken in the extraction liquid circulation tank 34 every 2 hours, after the oil-water phase separation by standing, the oil-phase extractant (P507) and the water-phase complexing agent (ammonium thiocyanate solution) were back-extracted, and the weight of cobalt and nickel obtained was measured, and the results are shown in table one, table two, and fig. 3 to 4.
Table one: variation of cobalt and nickel content in aqueous complexing agent
| Time (hours) | Cobalt content (mg) | Nickel content (mg) |
| 2 | 26.64 | - |
| 4 | 60.43 | - |
| 6 | 85.42 | - |
| 8 | 110.45 | - |
| 10 | 140.1 | - |
| 12 | 166.5 | 0.07 |
| 14 | 191.2 | 0.07 |
| 16 | 210.1 | 0.12 |
| 18 | 238.1 | 0.24 |
| 20 | 271.1 | 0.27 |
| 22 | 310 | 0.3 |
| 24 | 319.8 | 0.45 |
Table two: variation of cobalt and nickel content in oil phase extractant
| Time (hours) | Cobalt content (mg) | Nickel content (mg) |
| 2 | - | 20.1 |
| 4 | - | 50.1 |
| 6 | - | 80.1 |
| 8 | - | 95.55 |
| 10 | - | 106.4 |
| 12 | - | 120.5 |
| 14 | - | 139.1 |
| 16 | 0.033 | 165.5 |
| 18 | 0.075 | 180.5 |
| 20 | 0.089 | 191.22 |
| 22 | 0.105 | 211.1 |
| 24 | 0.175 | 217.6 |
As shown in table i, table ii and fig. 3-4, the cobalt content in the ammonium thiocyanate solution is greatly increased and the nickel content in P507 is greatly increased under the driving of the electric field, it can be seen that cobalt and nickel in the raw material tank 20 gradually enter the extraction tank 30 with time and are respectively combined with the ammonium thiocyanate solution and P507, and cobalt ions (as first metal ions in this embodiment) which are originally more easily extracted by P507 are combined with NH having stronger binding force4SCN complexes away, leaving nickel ions (as the second metal ions in this example) that are weakly bound to the ammonium thiocyanate solution positively charged and bound to P507. In this embodiment, aboutAfter 24 hours the cobalt was completely extracted, but some of the nickel was not completely extracted into P507.
Thus, after 24 hours of extraction, the feed tank 20 and holding tank 40 may be drained, and 400mL of 3.6N sulfuric acid may be introduced into the feed tank 20, and 400mL of 0.216N sulfuric acid may be introduced into the holding tank, followed by stripping for an additional 12 hours. In stripping, the nickel combined with the oil phase extractant in the extraction tank 30 is replaced and dissociated by the high concentration hydrogen ions from the raw material tank 20 passing through the first cation exchange membrane 52, and passes through the second cation exchange membrane 53 to the collection tank 40. On the other hand, the cobalt complex ion combined with the ammonium thiocyanate solution in the extraction tank 30 is confined in the extraction tank 30 by the first cation exchange membrane 52 and the second cation exchange membrane 53 on both sides. Although the back-extraction method of the electrodialysis has poor efficiency, the back-extraction method can be used for back-extracting nickel from the aqueous phase raw material solution with high cobalt and low nickel so as to further purify the cobalt.
According to the above results, the device for recovering metals by extraction with electrodialysis in conjunction with microemulsion according to the invention, by means of NH in aqueous phase4The SCN and the oil phase P507 are simultaneously and respectively complexed with cobalt and extracted nickel, so that mixed metal ions which are not easy to extract and separate by a solvent can be separated, and the purity and the value of the recovered metal are effectively improved. For example, when the solvent extraction is used to separate cobalt/nickel, the purity of the first-stage separation is about 70%, and the purity of the six-stage continuous countercurrent extraction is about 95%, compared with the present invention, the purity of the first-stage separation can reach 99.9%, and the extraction process does not need to be repeated many times, so that the extraction efficiency and purity can be greatly improved.
The foregoing is by way of example only, and not limiting. It is intended that all equivalent modifications or variations without departing from the spirit and scope of the present invention shall be included in the claims of the present application.
Claims (10)
1. An apparatus for recovering metals by electrodialysis in conjunction with microemulsion extraction, the apparatus comprising: a positive electrode tank containing an electrode liquid;
a raw material tank containing an aqueous solution containing a first metal ion and a second metal ion, wherein the first metal ion is a cobalt ion and the second metal ion is a nickel ion;
the extraction tank is accommodated with microemulsion, the microemulsion comprises ammonium thiocyanate solution, hexadecyl trimethyl ammonium bromide and oil phase extraction agent, wherein the binding force of the oil phase extraction agent to the first metal ions is smaller than that of the ammonium thiocyanate solution to the first metal ions, and the oil phase extraction agent is P507;
a collecting tank containing an electrolyte solution in which the second metal ions are soluble; and
the negative electrode groove is used for accommodating the electrode liquid and communicated with the positive electrode groove to provide potential difference; the anode tank, the raw material tank, the extraction tank, the collecting tank and the cathode tank are sequentially arranged and are respectively separated from one another by a first anion exchange membrane, a first cation exchange membrane, a second cation exchange membrane and a second anion exchange membrane in sequence, the raw material tank discharges the aqueous phase solution and is filled with a first acid solution, the collecting tank discharges the electrolyte solution and is filled with a second acid solution with the concentration smaller than that of the first acid solution, and the second metal ions are further limited in the extraction tank.
2. The device of claim 1, wherein said electrolyte solution has the same anion as said aqueous solution.
3. The apparatus of claim 1, wherein said microemulsion further comprises a surfactant for assisting oil-water mixing of said microemulsion.
4. The device of claim 3, wherein the surfactant comprises polyoxyethylene sorbitan oleate, sorbitan monooleate, quaternary ammonium salts of tetraoctylammonium lauryl sulfate, or any combination thereof.
5. The apparatus as claimed in claim 1, wherein the extraction tank is connected to an extraction liquid circulation tank to maintain the oil-water mixed state of the microemulsion in the extraction tank by means of circulation stirring.
6. The apparatus of claim 1, wherein said electrode fluid comprises a solution of a sodium or potassium salt of the same anion as said aqueous solution.
7. A method for metal recovery using the apparatus of claim 1, the method comprising: providing said potential difference to said anode cell and said cathode cell at a first predetermined time to perform an extraction procedure, said potential difference causing said first metal ion and said second metal ion to become localized in said extraction cell after passing from said feed cell through said first cation exchange membrane, wherein said first metal ion binds to an ammonium thiocyanate solution in said microemulsion and said second metal ion binds to an oil phase extractant in said microemulsion.
8. The method of claim 7, wherein the first predetermined time is a time at which the separation rate of the first metal ion and the second metal ion in the microemulsion is maximized.
9. The method of claim 8, further comprising after the extraction process is completed, allowing the ammonium thiocyanate solution and the oil phase extractant in the extraction tank to separate from each other, and removing the ammonium thiocyanate solution and the oil phase extractant separately for stripping to obtain the first metal ions and the second metal ions.
10. The method of claim 8, further comprising:
after the extraction procedure is finished, discharging the liquid in the raw material tank and the collecting tank, introducing a first acid solution into the raw material tank, and introducing a second acid solution with the concentration smaller than that of the first acid solution into the collecting tank; and
providing the potential difference to the anode tank and the cathode tank at a second predetermined time to allow the second metal ions in the oil phase extractant to pass through the second cation exchange membrane to enter the collecting tank,
wherein said first acid solution and said second acid solution have the same anion as said aqueous solution.
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| CN2292806Y (en) * | 1996-04-05 | 1998-09-30 | 中国科学院长春应用化学研究所 | Electrolytic extraction separation rare earth device |
| TWI551731B (en) * | 2015-11-30 | 2016-10-01 | 朝陽科技大學 | Method of metal recovering by electrodialysis synergized solvent extraction and apparatus thereof |
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| CN2292806Y (en) * | 1996-04-05 | 1998-09-30 | 中国科学院长春应用化学研究所 | Electrolytic extraction separation rare earth device |
| TWI551731B (en) * | 2015-11-30 | 2016-10-01 | 朝陽科技大學 | Method of metal recovering by electrodialysis synergized solvent extraction and apparatus thereof |
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