CN108239703A - A kind of electrochemical method and equipment for controlling bioleaching process - Google Patents
A kind of electrochemical method and equipment for controlling bioleaching process Download PDFInfo
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- CN108239703A CN108239703A CN201611203024.2A CN201611203024A CN108239703A CN 108239703 A CN108239703 A CN 108239703A CN 201611203024 A CN201611203024 A CN 201611203024A CN 108239703 A CN108239703 A CN 108239703A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- 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
The present invention provides a kind of electrochemical methods and equipment for controlling bioleaching process, it is in bioleaching process, by electrochemical control Leaching Systems oxidation-reduction potential, maintains pH value substantially constant, while copper-sulphide ores dissolving is not influenced, it can effectively inhibit the Quick Oxidation of pyrite.This method can accurately control oxidation-reduction potential in Leaching Systems, to realize that copper-sulphide ores Selectively leaching creates conditions.
Description
Technical field
The invention belongs to biological metallurgy fields, are related to a kind of electrochemical method for controlling bioleaching process.This method should
For the bioleaching process of the higher low-grade copper sulfide ores of pyrite content and the watershed management of acid wastewater in mine.
Background technology
With the continuous exploitation of mineral resources, valuable metal grade increasingly reduces, and recovery difficult continues to increase.Using copper mine as
Example, the copper grade verified mostly is less than 0.5%, and pyrite content is higher, economical can not be returned using traditional selecting and smelting technology
It receives.
In recent years, the biological metallurgy technology of research and development can solve the low technical barrier of the copper resource rate of recovery, but in leaching after
Phase acid, iron excess, subsequent solution purification and the raising of copper ion extraction cost, and environmental protection pressure increases.In addition, mining stripping
In barren rock, during long-term stockpiling, under the action of bacterium, water and oxygen, a large amount of acid waste water is generated, is the one of mine environmental protection
A especially big hidden danger.
Most sulphide ores are all semiconductors, and course of dissolution chemical reaction all carries out, and adjoint on mineral/electrolyte interface
The electric charge transfer by interface, sulphide ore semiconductor course of dissolution follows electrochemical mechanism.The presence of bacterium accelerates surface
The diffusion rate of substance and electronics enhances the reactivity worth of sulphide ore, promotes the oxidation reaction speed of mineral, corrosion reaction
Speed significantly improves, but bacterium does not have an impact the redox reaction process mechanism of sulphide ore electrode.Different crystal forms
Sulphide ore, dissolution mechanism is different, has different decomposition potentials in oxidative dissolving process.Pyrite lattice is relatively steady
Fixed, valence link is mainly formed by metallic atom track, and after surface loses electronics, M-S keys will not be destroyed, and only improves surface electricity
Position, valence link is just destroyed when reaching decomposition potential.And the valence link of copper-sulphide ores is by metallic atom and sulphur atom common rail shape
Into, as long as surface loses electronics, M-S keys will be destroyed.The decomposition potential of two class mineral has differences, in different oxidations
Rate of dissolution has differences under reduction potential.
Therefore, sulphide ore semiconductor sulphide ore biooxidation reactions follow electrochemical kinetics basic law, electrochemistry association
Same-action has decisive influence to sulphide ore course of dissolution.Therefore, the electrochemical method of bioleaching process how is controlled,
Under conditions of not influencing copper mine leaching rate, effectively inhibit the dissolving of pyrite, reducing sour iron generation rate becomes urgently to be resolved hurrily
Problem.
Invention content
To solve the above-mentioned problems, the object of the present invention is to provide it is a kind of control bioleaching process electrochemical apparatus,
Bioleaching process oxidation-reduction potential can be accurately controlled using the equipment, keeps pH value basicly stable, can effectively inhibit
Pyrite quickly dissolves, and realizes copper-sulphide ores Selectively leaching.
Another object of the present invention is to provide a kind of electrochemical reaction method for controlling bioleaching process, with reference to
Above equipment can effectively inhibit the dissolving of pyrite under conditions of copper mine leaching rate is not influenced, and reduce sour iron and generate rate.
To achieve these goals, the present invention is as follows using technical solution：
The present invention provides a kind of electrochemical apparatus for controlling bioleaching process, including an electrochemical cell and a control of Electric potentials
Device；Wherein, the electrochemical cell is for containing electrochemical reaction liquid, and passes through a partition board and be separated into two parts, and a part is anode
Reaction zone, another part are cathodic region, and a working electrode, an auxiliary electrode, a blender and one are equipped in the anode reaction area
Ventilation pipe is equipped with a reference electrode in the cathodic region；
The partition board is the partition board with cation-exchange membrane；
The working electrode is graphite electrode, positioned at anode reaction area close to the region of partition board；
The auxiliary electrode is platinum electrode, positioned at region of the anode reaction area far from partition board；
The blender is located at anode reaction district center, and blender bottom end is cross flabellum, for being stirred by flabellum rotation
Mixing is uniformly mixed electrochemical reaction liquid；
The ventilation pipe between the auxiliary electrode in anode reaction area and the cell wall of the electrochemical cell, the ventilation pipe
End is close to the bottom wall of the electrochemical cell；
The reference electrode is saturated calomel electrode, positioned at the region of cathodic region principle partition board；
The potentiometric controller is connect by electric wire with working electrode, auxiliary electrode and reference electrode respectively, for controlling sun
Oxidation-reduction potential between pole reaction zone and cathodic region.
The present invention separately provides a kind of electrochemical reaction method for controlling bioleaching process, includes the following steps：
1) provide one for controlling the electrochemical apparatus of bioleaching process, the electrochemical apparatus include an electrochemical cell and
One potentiometric controller；Wherein, which is separated into two parts by a partition board, a part of for anode reaction area, another portion
It is divided into cathodic region, a working electrode, an auxiliary electrode, a blender and a ventilation pipe, the moon is equipped in the anode reaction area
A reference electrode is equipped in polar region；
2) electrochemical reaction liquid is injected into the electrochemical cell, liquid level is higher than cation-exchange membrane 1-2mm, to cathodic region plus
Enter cultured mixed bacteria liquid, additive amount is the 20v/v% of electrochemical reaction liquid；
3) the copper-sulphide ores miberal powder of below 0.074mm accountings 80% is added to anode reaction area, is configured to a concentration of 5w/
The ore pulp solution of w%, is ventilated by the ventilation pipe, and oxygen is provided for bacterial growth, which is stirred, mixing speed
For 150rpm, the reaction time is 10~15 days；
Wherein, the ingredient of electrochemical reaction liquid is：The water for being 1.5 by the pH that 20v/v% sulfuric acid is prepared.
Preferably：By oxidation reduction potential control in the range of 650~760 (SHE).
Preferably, H+Can be by the cation-exchange membrane between cathode and anode region, control cathodic reaction zone pH values are
1.5~1.8.
Preferably, the preparation method of the copper-sulphide ores ore pulp solution is：Copper-sulphide ores are milled to -0.074mm accountings
More than 80%, it is added to the water and is configured to copper-sulphide ores ore pulp solution.
Preferably, the copper-sulphide ores are vitreous copper, covellite, blue vitreous copper or chalcopyrite.
Preferably, the ventilatory capacity of the ventilation pipe is 2~5L/m3/min。
Wherein, the Classification And Nomenclature of Thiobacillus thioxidans be Thiobacillus ferrooxidans Retech V, preservation
Unit is：China typical culture collection center, address：Wuhan, China Wuhan University, preservation date：On October 21st, 2002,
Deposit number：CCTCC NO：M202039；
Ferrous oxide hook end spirillum Classification And Nomenclature is Leptospirillum ferrooxidans Retech-SPL-1,
Depositary institution is：China typical culture collection center, address：Wuhan, China Wuhan University, preservation date：October 17 in 2008
Day, deposit number：CCTCC NO：M208162.
The preparation method of above-mentioned Mixed Microbes is：By the bacterium of preservation by rejuvenation, activity is improved, is then enlarged training again
Support, finally leached used in bacterium.
Culture medium prescription is：Low-grade vulcanization miberal powder 10.0g containing pyrite, zincblende；Sulphur powder 1.0g；(NH4) 2SO4
1.5g；K2HPO41.0g；KCl 0.1g；MgSO40.5g；Distilled water 1000mL, 121 DEG C of sterilizing 30min.
Rejuvenation：Thiobacillus thioxidans and ferrous oxide hook end spirillum are seeded in respectively in 200mL culture mediums, temperature is
30 DEG C, shaking table 120rpm, which is cultivated to bacteria concentration, is higher than 106A/mL.
Expand culture：The Thiobacillus thioxidans of rejuvenation and ferrous oxide hook end spirillum are inoculated in the medium respectively,
Inoculum concentration is respectively 5%, and temperature is 30 DEG C, and shaking table culture to bacteria concentration is higher than 106A/mL, then according to 1:After 1 ratio mixing
It accesses in reactive tank.
Method bonding apparatus provided by the invention can be by oxidation reduction potential control in the range of 650~760mV.
By electrochemical regulating and controlling method, oxidation-reduction potential in Leaching Systems is controlled, makes pH value substantially constant, inhibits yellow iron
Copper-sulphide ores Selectively leaching is realized in the quick dissolving of ore deposit.
The beneficial effects of the present invention are：
A kind of electrochemical reaction method and equipment for controlling bioleaching process of the present invention, this method and equipment energy
Enough make bioleaching process quantification controllable, realize copper-sulphide ores Selectively leaching.It reduces subsequent solution purification, be separated into
This, and sour iron yield can be greatly lowered, higher economic benefit can be generated.
Description of the drawings
Fig. 1 is the electrochemical apparatus schematic diagram of control bioleaching process provided by the invention.
Fig. 2 is to be gone back using the Leaching Systems oxidation of the electrochemical reaction method of control bioleaching process provided by the invention
Former current potential changes.
Fig. 3 is to be become using the Leaching Systems pH value of the electrochemical reaction method of control bioleaching process provided by the invention
Change curve.
Specific embodiment
SHE abridges for standard hydrogen electrode in the present invention, unit mV.
Electrochemical cell provided by the present invention is made with partition board of PVC material, and cation-exchange membrane is the height containing sulfonate radical
Molecular material (such as high density polyethylene (HDPE)), it only allows H+Through without solute is allowed to pass through.
The present invention program is further elaborated with reference to embodiments：
As shown in Figure 1, the electrochemical apparatus for control bioleaching process provided by the invention, including an electrochemical cell and
One potentiometric controller 7；Wherein, which is used to contain electrochemical reaction liquid, and pass through a partition board 5 and be separated into two parts,
A part is anode reaction area, and another part is cathodic region, and a working electrode 4, an auxiliary electrode are equipped in the anode reaction area
2nd, a blender 3 and a ventilation pipe 1 are equipped with a reference electrode 6 in the cathodic region；The partition board 5 is with cation-exchange membrane
The partition board of (such as sulfonic acid type density polyethylene film with high)；The working electrode 4 is graphite electrode, positioned at anode reaction area close to partition board
Region；The auxiliary electrode 5 is platinum electrode, positioned at region of the anode reaction area far from partition board；The blender 3 is located at anode reaction area
Center, blender bottom end are cross flabellum, are uniformly mixed electrochemical reaction liquid for passing through flabellum Stirring；The ventilation
Pipeline 1 is between the auxiliary electrode in anode reaction area and the cell wall of the electrochemical cell, and the end of the ventilation pipe is close to the electricity
The bottom wall of chemical tank；The reference electrode 6 is saturated calomel electrode, positioned at the region of cathodic region principle partition board；The potentiometric controller 7
It is connect respectively with working electrode, auxiliary electrode and reference electrode by electric wire, for controlling between anode reaction area and cathodic region
Oxidation-reduction potential.
Embodiment 1
The ore of use comes from Fujian low-grade copper sulfide ores, and copper is mainly deposited in the form of vitreous copper and covellite in ore
Pyrite content is higher, and gangue mineral mainly exists with silicate patterns, and acid consumption is relatively low.Ore essential element analysis knot
Fruit is shown in Table 1.
1 essential element chemical analysis results of table
| Cu | Fe | S | SiO2 | |
| Content/wt% | 0.35 | 3.52 | 3.81 | 79.28 |
Tap water is added in electrochemical cell first, by the use of the acid water that 20v/v% sulfuric acid secure ph is 1.50 as electrochemical
Reaction solution is learned, adds in anode region and cathodic reaction zone, then cultured Mixed Microbes are accessed in cathodic region, inoculum concentration is 20% (v/
V), the miberal powder that -74 microns of accountings are more than 80% is then added in, preparations pulp density is 5% (w/w), and blowing air, ventilatory capacity control
System is in 4L/min, and mixing speed 150rpm, temperature is room temperature, and control oxidation-reduction potential is 740mV, 15 days reaction time.
Leaching test the results are shown in Table 2 and Fig. 2, Fig. 3.
2 copper and iron leaching test result of table
| Extraction time/d | 4 | 8 | 12 | 16 |
| Cu leaching rates/% | 40.24 | 60.75 | 72.58 | 80.12 |
| Fe leaching rates/% | 6.24 | 8.18 | 9.26 | 10.12 |
, can be effectively by control of Electric potentials in 730mV by using the method for the present invention, and H+Pass through cation-exchange membrane and the moon
Polar region reaches balance, and pH value is controlled substantially 1.50, keeps bacterium Steady breed.By controlling current potential, pyrite is effectively inhibited
Quick dissolving, leach 16 days, iron has leached only 10.12%, and copper leaching rate reaches 80.12%.It is thereby achieved that vulcanization
Copper mine Selectively leaching.
Embodiment 2
The ore of use comes from Xinjiang low-grade copper sulfide ores, and copper is mainly deposited in the form of vitreous copper and chalcopyrite in ore
Pyrite content is higher, and gangue mineral mainly exists with silicate patterns, and acid consumption is relatively low.Ore essential element analysis knot
Fruit is shown in Table 3.
3 essential element chemical analysis results of table
| Cu | Fe | S | SiO2 | |
| Content/wt% | 0.45 | 3.61 | 3.71 | 80.12 |
Tap water is added in electrochemical cell first, by the use of the acid water that 20v/v% sulfuric acid secure ph is 1.50 as electrochemical
Reaction solution is learned, adds in anode region and cathodic reaction zone, then cultured Mixed Microbes are accessed in cathodic region, inoculum concentration is 20% (v/
V), the miberal powder that -74 microns of accountings are more than 80% is then added in, preparation pulp density is 5% (w/w), and is ventilated, ventilatory capacity control
In 3L/min, mixing speed 150rpm, temperature is room temperature, control oxidation-reduction potential be 700mV, 15 days reaction time.Leaching
Go out result of the test and be shown in Table 4.
4 copper and iron leaching test result of table
| Extraction time/d | 4 | 8 | 12 | 16 |
| Cu leaching rates/% | 38.18 | 58.45 | 68.49 | 76.69 |
| Fe leaching rates/% | 5.34 | 7.38 | 8.86 | 9.78 |
, can be effectively by control of Electric potentials in 710mV by using the method for the present invention, and H+Pass through cation-exchange membrane and the moon
Polar region reaches balance, and pH value is controlled substantially 1.80, keeps bacterium Steady breed.By controlling current potential, pyrite is effectively inhibited
Quick dissolving, leach 16 days, iron has leached only 9.78%, and copper leaching rate reaches 76.69%.It is thereby achieved that vulcanization
Copper mine Selectively leaching.
Controlling leaching process oxidation-reduction potential by electrochemical regulating and controlling method, pH value 1.5~1.8 is realized less than 760mV
Current potential and pH value Rational Matching of Parameters, inhibit the leaching of pyrite, slow down the accumulation of sour iron.
From above-described embodiment as can be seen that the electrochemical reaction device and method, can maintain the pH of Bioleaching system
Stablize, while copper-sulphide ores dissolving is not influenced, can effectively inhibit the Quick Oxidation of pyrite.This method can be controlled accurately
Oxidation-reduction potential in Leaching Systems, to realize that copper-sulphide ores Selectively leaching creates conditions.
Claims (10)
1. a kind of electrochemical apparatus for controlling bioleaching process, which is characterized in that including an electrochemical cell and a control of Electric potentials
Device；Wherein, the electrochemical cell is for containing electrochemical reaction liquid, and passes through a partition board and be separated into two parts, and a part is anode
Reaction zone, another part are cathodic region, and a working electrode, an auxiliary electrode, a blender and one are equipped in the anode reaction area
Ventilation pipe is equipped with a reference electrode in the cathodic region；
The partition board lower half is provided with reticulated cell, and netted hole surface is covered with cation-exchange membrane；
The working electrode is graphite electrode, positioned at anode reaction area close to the region of partition board；
The auxiliary electrode is platinum electrode, positioned at region of the anode reaction area far from partition board；
The blender is located at anode reaction district center, and blender bottom end is cross flabellum, is made for passing through flabellum Stirring
Electrochemical reaction liquid is uniformly mixed；
The ventilation pipe is between the auxiliary electrode in anode reaction area and the cell wall of the electrochemical cell, the end of the ventilation pipe
Close to the bottom wall of the electrochemical cell, for providing sufficient oxygen for reaction system；
The reference electrode is saturated calomel electrode, positioned at region of the cathodic region far from partition board；
The potentiometric controller is connect by electric wire with working electrode, auxiliary electrode and reference electrode respectively, for controlling anode anti-
Answer the oxidation-reduction potential between area and cathodic region.
2. a kind of electrochemical reaction method for controlling bioleaching process, which is characterized in that include the following steps：
1) electrochemical apparatus for being used to control bioleaching process as described in claim 1, the electrochemical apparatus packet are provided
Include an electrochemical cell and a potentiometric controller；Wherein, which is separated into two parts by a partition board, and a part is anode
Reaction zone, another part are cathodic region, and a working electrode, an auxiliary electrode, a blender and one are equipped in the anode reaction area
Ventilation pipe is equipped with a reference electrode in the cathodic region；
2) electrochemical reaction liquid is injected into the electrochemical cell, liquid level is higher than cation-exchange membrane 1-2mm, adds in and trains to cathodic region
The mixed bacteria liquid supported, additive amount are the 20v/v% of electrochemical reaction liquid；
3) the copper-sulphide ores miberal powder of below 0.074mm accountings 80% is added to anode reaction area, is configured to a concentration of 5w/w%
Ore pulp solution, ventilated by the ventilation pipe, oxygen provided for bacterial growth, which is stirred, and mixing speed is
150rpm；Reaction time is 10~15 days；
Wherein, the ingredient of electrochemical reaction liquid is：The water for being 1.5 by the pH that 20v/v% sulfuric acid is prepared.
3. a kind of electrochemical reaction method for controlling bioleaching process according to claim 2, which is characterized in that by oxygen
Change reduction potential control in 650~760mV.
4. a kind of electrochemical method for controlling bioleaching process according to claim 2, which is characterized in that by additional
20v/v% sulfuric acid control cathodic reaction zone pH value is 1.5~1.8.
5. a kind of electrochemical reaction method for controlling bioleaching process according to claim 2, which is characterized in that described
The preparation method of copper-sulphide ores ore pulp solution is：Copper-sulphide ores are milled to -74 mesh accountings more than 80%, be added to the water preparation
Into copper-sulphide ores ore pulp solution.
6. a kind of electrochemical reaction method for controlling bioleaching process according to claim 2, which is characterized in that described
Copper-sulphide ores are vitreous copper, covellite, blue vitreous copper or chalcopyrite.
7. a kind of electrochemical reaction method for controlling bioleaching process according to claim 2, which is characterized in that described
The ventilatory capacity of ventilation pipe is 2~5L/m of ventilatory capacity3/min。
8. a kind of electrochemical reaction method for controlling bioleaching process according to claim 2, which is characterized in that described
Mixed Microbes are Thiobacillus thioxidans and ferrous oxide hook end spirillum with 1：1 mixes；
Wherein, the Classification And Nomenclature of Thiobacillus thioxidans be Thiobacillus ferrooxidans Retech V, depositary institution
For：China typical culture collection center, address：Wuhan, China Wuhan University, preservation date：On October 21st, 2002, preservation
Number：CCTCC NO：M202039；
Ferrous oxide hook end spirillum Classification And Nomenclature be Leptospirillum ferrooxidans Retech-SPL-1, preservation
Unit is：China typical culture collection center, address：Wuhan, China Wuhan University, preservation date：On October 17th, 2008,
Deposit number：CCTCC NO：M208162.
9. a kind of electrochemical reaction method for controlling bioleaching process according to claim 8, which is characterized in that described
The rejuvenation of Thiobacillus thioxidans and ferrous oxide hook end spirillum, the culture medium of expansion culture are：Culture medium prescription is：Containing yellow iron
The low-grade vulcanization miberal powder 10.0g of ore deposit, zincblende；Sulphur powder 1.0g；(NH4) 2SO41.5g；K2HPO41.0g；KCl 0.1g；
MgSO40.5g；Distilled water 1000mL, 121 DEG C of sterilizing 30min.
A kind of 10. electrochemical reaction method for controlling bioleaching process according to claim 8, which is characterized in that oxygen
The rejuvenation for changing sulphur Thiobacillus and ferrous oxide hook end spirillum, the method for expanding culture are：
Rejuvenation：Thiobacillus thioxidans and ferrous oxide hook end spirillum are seeded in respectively in 200mL culture mediums, temperature 30
DEG C, shaking table 120rpm, which is cultivated to bacteria concentration, is higher than 106A/mL；
Expand culture：The Thiobacillus thioxidans of rejuvenation and ferrous oxide hook end spirillum are inoculated in the medium respectively, inoculation
Amount is respectively 5%, and temperature is 30 DEG C, and shaking table culture to bacteria concentration is higher than 106A/mL.
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| CN108998668A (en) * | 2018-08-24 | 2018-12-14 | 中南大学 | A method of regulation high-iron sphalerite dissolution |
| CN109628357A (en) * | 2019-02-12 | 2019-04-16 | 黑龙江八农垦大学 | A kind of ferrous oxide complex microbial inoculum and its application |
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| CN108998668A (en) * | 2018-08-24 | 2018-12-14 | 中南大学 | A method of regulation high-iron sphalerite dissolution |
| CN108998668B (en) * | 2018-08-24 | 2020-01-31 | 中南大学 | method for regulating and controlling dissolution of high-iron sphalerite |
| CN109628357A (en) * | 2019-02-12 | 2019-04-16 | 黑龙江八农垦大学 | A kind of ferrous oxide complex microbial inoculum and its application |
| CN112080637A (en) * | 2020-08-24 | 2020-12-15 | 中国科学院微生物研究所 | Photoelectric energy method for promoting microbial Ar-4 biological metallurgy leaching rate |
| CN113122882A (en) * | 2021-06-16 | 2021-07-16 | 中南大学 | Ore pulp battery |
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