CN115747478A - Method for realizing gas recycling in cobalt production process - Google Patents
Method for realizing gas recycling in cobalt production process Download PDFInfo
- Publication number
- CN115747478A CN115747478A CN202211435631.7A CN202211435631A CN115747478A CN 115747478 A CN115747478 A CN 115747478A CN 202211435631 A CN202211435631 A CN 202211435631A CN 115747478 A CN115747478 A CN 115747478A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- gas
- organic phase
- water
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 75
- 239000010941 cobalt Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000012074 organic phase Substances 0.000 claims abstract description 54
- 239000007789 gas Substances 0.000 claims abstract description 50
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000000605 extraction Methods 0.000 claims abstract description 43
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 28
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 28
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 14
- 238000007127 saponification reaction Methods 0.000 claims abstract description 14
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 12
- 239000011028 pyrite Substances 0.000 claims abstract description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 238000005188 flotation Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000007654 immersion Methods 0.000 claims abstract description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 34
- 239000000428 dust Substances 0.000 claims description 26
- 239000000779 smoke Substances 0.000 claims description 23
- 239000012141 concentrate Substances 0.000 claims description 17
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 11
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000001180 sulfating effect Effects 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000008236 heating water Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- NMLUQMQPJQWTFK-UHFFFAOYSA-N arsanylidynecobalt Chemical compound [As]#[Co] NMLUQMQPJQWTFK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for realizing gas recycling in a cobalt production process, and belongs to the technical field of cobalt production. Preparing tailings and a mixed solution A by sulfating roasting leaching after flotation of the pyrite containing cobalt, extracting the mixed solution A through P204 and P507 in sequence to obtain a cobalt chloride solution, electrolytically depositing cobalt by using part of cobalt chloride, and calcining the precipitated cobalt carbonate by using the other part of cobalt chloride to prepare cobalt powder; the heat of the calcined gas is used for heating water immersion, and sulfur dioxide in the gas and reduction leaching are used for preparing sulfuric acid; heating ammonium chloride crystals by using the calcination heat of the cobalt carbonate to generate ammonia gas, hydrogen chloride and water vapor, preparing sulfuric acid by using the water vapor, using solvent water for reuse water in the water leaching step, using the ammonia gas for saponification of a poor organic phase and preparing ammonium bicarbonate by using the ammonia gas and carbon dioxide generated by calcination, and using the hydrogen chloride for back extraction of a cobalt-containing organic phase; hydrogen generated by electrolysis is used for reduction during cobalt carbonate calcination; the whole process fully utilizes gas heat energy, and partial byproducts are returned to the process for utilization, thereby saving energy and protecting environment.
Description
Technical Field
The invention belongs to the technical field of cobalt production, and relates to a method for realizing gas recycling in a cobalt production process.
Background
Cobalt is an important strategic resource, plays an important role in the high-tech fields such as national defense, lithium batteries and the like, and has a continuously increased value with the rise of new energy automobiles in recent years, so that the development of the cobalt resource has a higher economic value, and people need to vigorously research and develop the process of low-grade cobalt-containing ores with the increasing exhaustion of the cobalt resource. Cobalt ore exists alone rarely in nature, mainly accompanies nickel ore, copper ore, pyrite and arsenic deposit, and has less content and relatively difficult extraction, cobalt ore resources mainly comprise four types of nickel-cobalt sulfide ore and oxide ore, copper-cobalt ore, arsenic-cobalt ore and cobalt-containing pyrite, and cobalt smelting characteristics are represented by low raw material grade, long extraction flow and more extraction methods.
The traditional process for extracting cobalt from the cobalt-containing pyrite comprises the following steps: the method comprises the steps of preparing cobalt-sulfur concentrate from pyrite containing cobalt through flotation, carrying out sulfating roasting on the cobalt-sulfur concentrate to convert valuable elements such as cobalt, nickel and copper in the cobalt-sulfur concentrate into soluble sulfate, and leaching the roasted product with water or acid to convert the cobalt, nickel and copper into a solution. The leachate is purified to remove impurities such as copper, zinc and the like, and then the pure cobalt solution is obtained through nickel-cobalt separation, and the metal cobalt is produced through electrodeposition. However, in the traditional process, a large amount of heat in steam generated by roasting is not fully utilized, so that waste is caused, a large amount of electric energy is consumed for preparing cobalt by an electrodeposition method, meanwhile, chlorine generated in the cobalt preparation process by the electrodeposition method is also a problem to be solved, and a large amount of waste liquid is generated in the purification step of leachate, so that the problem of environmental pollution is caused. Therefore, research and improvement of the process for preparing cobalt from the pyrite containing cobalt can fully utilize steam and heat energy generated in the process, promote the whole process to reduce external emission, save energy and protect environment, and is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a method for realizing gas recycling in a cobalt production process, and belongs to the technical field of cobalt production. The method comprises the steps of carrying out sulfating roasting leaching on the floated pyrite containing cobalt to prepare tailings containing ferric oxide and a mixed solution A, wherein the mixed solution A is subjected to P204 extraction and P507 extraction to obtain a cobalt chloride solution, one part of the cobalt chloride solution is electrolyzed and deposited to prepare cobalt, and the other part of the cobalt chloride solution is used for precipitating cobalt carbonate and is further calcined in a hydrogen atmosphere to prepare cobalt powder; heating the water leaching treatment step by utilizing the heat of gas generated by calcining the pyrite containing cobalt, preparing sulfuric acid by utilizing sulfur trioxide, sulfur dioxide and water vapor in the gas and preparing the sulfuric acid by reducing water leaching, and returning the sulfuric acid to the process for use; heating ammonium chloride crystals by using the heat of cobalt carbonate calcination to generate ammonia gas, hydrogen chloride and water vapor, wherein the water vapor is used for preparing sulfuric acid, the ammonia gas is used for saponifying a lean organic phase and preparing ammonium bicarbonate with carbon dioxide generated by cobalt carbonate calcination, the hydrogen chloride is used for back extraction of a cobalt-containing organic phase, and solvent water in an ammonium chloride solution is used as reuse water in a water leaching step; hydrogen generated in the electrolytic process is used for reducing the cobalt carbonate calcination; the whole process fully utilizes the heat energy of the gas, and meanwhile, part of byproducts are returned to the process for utilization, so that the energy is saved and the environment is protected.
The purpose of the invention can be realized by the following technical scheme:
a method for realizing gas recycling in a cobalt production process comprises the following steps:
(1) Preparing cobalt-sulfur concentrate from the cobalt-containing pyrite through flotation, uniformly mixing the cobalt-sulfur concentrate and a sulfuric acid solution, placing the mixture into a roasting furnace for roasting, and producing roasted sand, smoke dust and gas containing sulfur dioxide, sulfur trioxide and water vapor after roasting;
(2) Discharging the calcine, adding reuse water for water leaching treatment, and filtering to obtain tailings mainly containing ferric oxide and a mixed solution A containing cobalt sulfate, nickel sulfate, copper sulfate and zinc sulfate;
(3) Extracting the mixed solution A by P204 extraction equipment to obtain a mixed solution B containing cobalt sulfate and nickel sulfate and a loaded organic phase 1 containing copper ions, zinc ions and the like;
(4) Adding a sulfuric acid solution into the loaded organic phase 1 to wash cobalt to obtain a mixed solution C containing a small amount of cobalt sulfate and nickel sulfate and a loaded organic phase 2 containing copper ions, zinc ions and the like, adding sulfuric acid into the loaded organic phase 2 to perform back extraction to obtain a mixed solution D containing copper sulfate and zinc sulfate and a poor organic phase 1, wherein the mixed solution D is used for recovering copper and zinc, and the poor organic phase 1 is continuously used for extraction in a P204 extraction device after being saponified by adding alkali;
(5) Extracting the mixed solution B obtained in the step (3) and the mixed solution C obtained in the step (4) by P507 extraction equipment to obtain a cobalt-containing organic phase and a raffinate containing nickel sulfate, wherein the raffinate is used for recovering nickel;
(6) Adding a hydrochloric acid solution into the cobalt-containing organic phase for back extraction to obtain a cobalt chloride solution and a lean organic phase 2, adding alkali into the lean organic phase 2 for saponification, and then continuously using the lean organic phase in P507 extraction equipment for extraction;
(7) Preparing cobalt from a part of cobalt chloride solution by an electrolytic deposition method, and simultaneously generating chlorine and a small amount of by-product hydrogen;
(8) And adding the other part of the cobalt chloride solution into an ammonium bicarbonate solution to prepare precipitated cobalt carbonate, simultaneously generating an ammonium chloride solution, filtering, putting the cobalt carbonate into a calcining furnace, and calcining in a hydrogen atmosphere to prepare cobalt powder.
The contents of main elements in the cobalt-sulfur concentrate obtained by flotation of the cobalt-containing pyrite are shown in the following table 1:
TABLE 1 content of main elements in cobalt-sulfur concentrate
| Serial number | Element(s) | Content (%) |
| 1 | Co | 0.628 |
| 2 | Ni | 0.059 |
| 3 | Cu | 0.921 |
| 4 | Fe | 31.947 |
| 5 | S | 33.452 |
| 6 | Zn | 0.024 |
| 7 | H 2 O | 0.352 |
As a preferable technical scheme of the invention, the roasting temperature in the step (1) is 610-630 ℃, and the roasting time is 2-4h. After roasting at the optimized temperature and time, the iron element in the cobalt-sulfur concentrate is converted into ferric oxide, the sulfur element is oxidized into sulfur dioxide and sulfur trioxide to enter smoke dust and gas, and the water in the cobalt-sulfur concentrate is converted into water vapor to enter the gas.
As a preferable technical scheme of the invention, the temperature of the water leaching treatment in the step (2) is 70-90 ℃, the water leaching treatment time is 4-6h, the liquid-solid ratio of the water leaching treatment is 2-4. And (3) leaching the roasted calcine by water to obtain tailings and a mixed solution A, wherein ferric oxide enters the tailings, and the mixed solution A contains cobalt ions, nickel ions, copper ions, zinc ions and the like.
As a preferable technical scheme of the invention, the current density of the electrolytic deposition method in the step (7) is 300-400A/m 2 The cell voltage is 2-3V.
As a preferable technical scheme of the invention, the calcining temperature of the cobalt carbonate in the step (8) in a hydrogen atmosphere is 400-600 ℃, and the calcining time is 3-5h.
As a preferred technical scheme of the invention, a heat exchanger 1 is arranged outside the roasting furnace in the step (1), high-temperature smoke dust and gas generated in the roasting process are replaced by low-temperature smoke dust and gas, the low-temperature smoke dust and gas comprise smoke dust, sulfur trioxide, sulfur dioxide and water vapor, the smoke dust is collected by cyclone, cloth bag and electric dust collection, and the sulfur trioxide, sulfur dioxide are subjected to catalytic oxidation and the water vapor is used for preparing sulfuric acid; and (3) replacing the low-temperature reuse water with high-temperature reuse water by the heat exchanger 1 for water leaching treatment in the step (2), wherein the water leaching treatment is carried out in a reaction kettle with a coil pipe device.
As a preferred technical scheme of the invention, the sulfuric acid prepared from sulfur trioxide, sulfur dioxide and water vapor is purified and then used for washing cobalt in the loaded organic phase 1 and back extraction of the loaded organic phase 2 in the step (4) and roasting in the step (1).
As a preferable technical scheme of the invention, chlorine generated in the electrolytic deposition process in the step (7) is collected and used for leaching, oxidizing and removing impurities.
As a preferable technical scheme of the invention, the byproduct hydrogen in the step (7) is collected and then used for calcining the cobalt carbonate in the step (8) to prepare cobalt powder.
As a preferable technical scheme of the invention, a heat exchanger 2 is arranged outside the calcining furnace in the step (8), the high-temperature carbon dioxide gas generated after the cobalt carbonate calcination is replaced by the low-temperature carbon dioxide gas through a heat exchanger 2, the low-temperature ammonium chloride solution is replaced by the high-temperature ammonium chloride solution through the heat exchanger 2, ammonium chloride crystals are promoted to decompose to generate ammonia gas, hydrogen chloride and water vapor, the water vapor is used for preparing sulfuric acid, the ammonia gas is used for the alkali-adding saponification of the organic-poor phase 1 in the step (4) and the alkali-adding saponification of the organic-poor phase 2 in the step (6) and is used for preparing ammonium bicarbonate with the carbon dioxide generated by the cobalt carbonate calcination, the hydrogen chloride is dissolved in water to prepare a hydrochloric acid solution for the back extraction of the cobalt-containing organic phase in the step (6), and the solvent water in the ammonium chloride solution is used for the reuse water in the water leaching step.
The invention has the beneficial effects that:
(1) The invention replaces the high-temperature smoke dust and gas generated in the roasting process into low-temperature smoke dust and gas through the heat exchanger 1, the heat of the low-temperature smoke dust and gas is used for replacing low-temperature reuse water into high-temperature reuse water for water immersion treatment in the step (2), the heat generated in the roasting process is fully utilized, and meanwhile, the stability of the temperature in the roasting furnace is controlled;
(2) The method purifies sulfuric acid prepared from sulfur trioxide, sulfur dioxide and water vapor generated in the roasting process, and then the sulfuric acid is used for cobalt washing of the loaded organic phase 1 and back extraction of the loaded organic phase 2 in the step (4) and roasting in the step (1), so that the outward emission of harmful gas is prevented, and meanwhile, raw materials are saved for subsequent cobalt washing, back extraction and front-end roasting steps, and the method is energy-saving and environment-friendly;
(3) Chlorine generated in the electrolytic deposition process is collected and then used for leaching, oxidizing and removing impurities, so that the emission of harmful gas is reduced, hydrogen chloride is generated in the decomposition process of ammonium chloride crystals, and the hydrogen chloride is dissolved in water to prepare a hydrochloric acid solution for back extraction of the cobalt-containing organic phase in the step (6), so that the emission of waste liquid is reduced, and meanwhile, a raw material is provided for the subsequent back extraction process;
(4) Ammonia gas generated by decomposing the ammonium chloride crystals is used for alkali saponification of the poor organic phase 1 in the step (4), alkali saponification of the poor organic phase 2 in the step (6) and preparation of ammonium bicarbonate with carbon dioxide generated by calcining cobalt carbonate, and is recycled in the process, so that waste liquid discharge is reduced, and meanwhile, saponification regeneration of the poor organic phase of the subsequent P204 extraction and the poor organic phase of the P507 extraction is promoted;
(5) The invention uses the water vapor generated in the water leaching step and the water vapor generated by decomposing the ammonium chloride crystal to prepare the sulfuric acid, and the sulfuric acid is purified and reused in the process; the solvent water in the ammonium chloride solution is used as reuse water in the water leaching step, so that water waste is avoided, and water resources are saved;
(6) According to the invention, the heat of the carbon dioxide gas generated in the cobalt carbonate calcining process is replaced by the heat exchanger 2, and the heat is used for preparing ammonia gas and hydrogen chloride by decomposing ammonium chloride crystals, so that the heat is recycled, and the energy-saving and environment-friendly effects are achieved.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be provided in conjunction with the embodiments.
Example 1
A method for realizing gas recycling in a cobalt production process comprises the following steps:
(1) Preparing cobalt-sulfur concentrate from cobalt-containing pyrite through flotation, uniformly mixing the cobalt-sulfur concentrate and a sulfuric acid solution, placing the mixture in a roasting furnace, roasting at 620 ℃ for 3 hours, producing roasted sand and smoke dust and gas containing sulfur dioxide, sulfur trioxide and water vapor after roasting, converting iron elements in the cobalt-sulfur concentrate into ferric oxide, oxidizing the sulfur elements into sulfur trioxide and sulfur dioxide, enabling the sulfur trioxide and the sulfur dioxide to enter the smoke dust and gas, and converting water in the cobalt-sulfur concentrate into water vapor and enabling the water vapor to enter the gas;
(2) Adding reuse water into the discharged calcine, carrying out water leaching treatment for 5 hours at the temperature of 80 ℃, wherein the water leaching treatment is carried out in a reaction kettle with a coil pipe device, the solid-to-liquid ratio of the water leaching is controlled to be 3; arranging a heat exchanger 1 outside the roasting furnace, replacing high-temperature smoke dust and gas generated in the roasting process with low-temperature smoke dust and gas, wherein the low-temperature smoke dust and gas comprise smoke dust, sulfur trioxide, sulfur dioxide and water vapor, collecting the smoke dust through cyclone, cloth bag and electric dust collection, and catalytically oxidizing the sulfur trioxide and the sulfur dioxide and using the water vapor to prepare sulfuric acid; replacing low-temperature reuse water with high-temperature reuse water by the heat exchanger 1 for water leaching treatment in the step (2); purifying sulfuric acid prepared from sulfur trioxide, sulfur dioxide and water vapor, and then using the purified sulfuric acid in the step (4) to wash cobalt in the loaded organic phase 1 and the loaded organic phase 2 for back extraction and roasting in the step (1);
(3) Extracting the mixed solution A by P204 extraction equipment to obtain a mixed solution B containing cobalt sulfate and nickel sulfate and a loaded organic phase 1 containing copper ions, zinc ions and the like;
(4) Adding a sulfuric acid solution into the loaded organic phase 1 to wash cobalt to obtain a mixed solution C containing a small amount of cobalt sulfate and nickel sulfate and a loaded organic phase 2 containing copper ions, zinc ions and the like, adding sulfuric acid into the loaded organic phase 2 to perform back extraction to obtain a mixed solution D containing copper sulfate and zinc sulfate and a lean organic phase 1, wherein the mixed solution D is used for recovering copper and zinc, and the lean organic phase 1 is continuously used for extraction in a P204 extraction device after being saponified by adding alkali;
(5) Extracting the mixed solution B obtained in the step (3) and the mixed solution C obtained in the step (4) by P507 extraction equipment to obtain a cobalt-containing organic phase and a raffinate containing nickel sulfate, wherein the raffinate is used for recovering nickel;
(6) Adding a hydrochloric acid solution into the cobalt-containing organic phase for back extraction to obtain a cobalt chloride solution and a lean organic phase 2, adding alkali into the lean organic phase 2 for saponification, and then continuously using a P507 extraction device for extraction;
(7) Preparing cobalt from 78% cobalt chloride solution by electrolytic deposition method with current density of 350A/m 2 The cell voltage is 3V, chlorine and a small amount of by-product hydrogen are generated simultaneously, and the chlorine is collected and used for leaching, oxidizing and removing impurities; after being collected, the hydrogen is used for calcining the cobalt carbonate in the step (8) to prepare cobalt powder;
(8) Adding 22% cobalt chloride solution into ammonium bicarbonate solution and nucleating agent to prepare precipitated cobalt carbonate, simultaneously generating ammonium chloride solution, filtering, putting the cobalt carbonate into a calcining furnace, and calcining at 500 ℃ for 4h in hydrogen atmosphere to prepare cobalt powder; a heat exchanger 2 is arranged outside the calcining furnace, high-temperature carbon dioxide gas generated after the cobalt carbonate is calcined is replaced by low-temperature carbon dioxide gas through a heat exchanger 2, a catalyst is added into the low-temperature ammonium chloride solution, the low-temperature ammonium chloride solution is replaced by high-temperature ammonium chloride solution through the heat exchanger 2, ammonium chloride crystals are promoted to be decomposed to generate ammonia gas, hydrogen chloride and water vapor, the ammonia gas is used for alkali saponification of the poor organic phase 1 in the step (4), alkali saponification of the poor organic phase 2 in the step (6) and preparation of ammonium bicarbonate through the carbon dioxide generated by calcining the cobalt carbonate, the hydrogen chloride is dissolved in water to prepare hydrochloric acid solution, the hydrochloric acid solution is used for back extraction of the cobalt-containing organic phase in the step (6), the water vapor is used for preparing sulfuric acid, and the solvent water in the ammonium chloride solution is used for reuse water in the water leaching step.
The total investment of the project implementation of the embodiment is 50 ten thousand yuan, and the total investment is calculated through actual test operationThe water vapor in the cobalt-sulfur concentrate can be used for 326.47t; water can be saved by 7412.3t every year, sulfur dioxide is produced by 8975.35t every year in the roasting stage of the cobalt-sulfur concentrate, and the utilization rate of the sulfur dioxide reaches 98.5 percent; 684.21t of chlorine gas is annually produced in the cobalt stage prepared by an electrolytic deposition method, and the utilization rate of the chlorine gas reaches 99.1 percent; 38.7t of hydrogen produced annually in the cobalt stage prepared by the electrolytic deposition method, wherein the utilization rate of the hydrogen reaches 99.6 percent; ammonia gas is produced for 158.23t every year in the cobalt carbonate precipitation stage, and the utilization rate of the ammonia gas reaches 99.5 percent; the annual production of 335.08t of hydrogen chloride in the cobalt carbonate precipitation stage reaches the utilization rate of 99.8 percent; the annual production of carbon dioxide at 267.28t in the cobalt carbonate calcining stage reaches the utilization rate of 95.2 percent; through the arrangement of the heat exchanger 1 and the heat exchanger 2, the annual energy consumption is saved by 3.152 multiplied by 10 10 kJ; the yield of the cobalt reaches 94.58 percent, and the purity of the cobalt reaches 99.55 percent.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for realizing gas recycling in a cobalt production process is characterized by comprising the following steps:
(1) Preparing cobalt-sulfur concentrate from the cobalt-containing pyrite through flotation, uniformly mixing the cobalt-sulfur concentrate and a sulfuric acid solution, placing the mixture into a roasting furnace for roasting, and producing roasted sand, smoke dust and gas containing sulfur dioxide, sulfur trioxide and water vapor after roasting;
(2) Discharging the calcine, adding reuse water for water leaching treatment, and filtering to obtain tailings mainly containing ferric oxide and a mixed solution A containing cobalt sulfate, nickel sulfate, copper sulfate and zinc sulfate;
(3) Extracting the mixed solution A by P204 extraction equipment to obtain a mixed solution B containing cobalt sulfate and nickel sulfate and a loaded organic phase 1 containing copper ions, zinc ions and the like;
(4) Adding a sulfuric acid solution into the loaded organic phase 1 to wash cobalt to obtain a mixed solution C containing cobalt sulfate and nickel sulfate and a loaded organic phase 2 containing copper ions, zinc ions and the like, adding sulfuric acid into the loaded organic phase 2 to perform back extraction to obtain a mixed solution D containing copper sulfate and zinc sulfate and a lean organic phase 1, wherein the mixed solution D is used for recovering copper and zinc, and the lean organic phase 1 is subjected to alkali saponification and then is continuously used for extraction by a P204 extraction device;
(5) Extracting the mixed solution B obtained in the step (3) and the mixed solution C obtained in the step (4) by P507 extraction equipment to obtain a cobalt-containing organic phase and a raffinate containing nickel sulfate, wherein the raffinate is used for recovering nickel;
(6) Adding a hydrochloric acid solution into the cobalt-containing organic phase for back extraction to obtain a cobalt chloride solution and a lean organic phase 2, adding alkali into the lean organic phase 2 for saponification, and then continuously using the lean organic phase in P507 extraction equipment for extraction;
(7) Preparing cobalt from part of cobalt chloride solution by an electrolytic deposition method, and simultaneously generating chlorine and a byproduct hydrogen;
(8) And adding the other part of the cobalt chloride solution into an ammonium bicarbonate solution to prepare precipitated cobalt carbonate, simultaneously generating an ammonium chloride solution, filtering, putting the cobalt carbonate into a calcining furnace, and calcining in a hydrogen atmosphere to prepare cobalt powder.
2. The method for recycling gas in the cobalt production process according to claim 1, wherein the roasting temperature in the step (1) is 610-630 ℃, and the roasting time is 2-4h.
3. The method for recycling gas in the cobalt production process according to claim 1, wherein the water leaching treatment in the step (2) is carried out at a temperature of 70-90 ℃ for 4-6h, the liquid-solid ratio of the water leaching treatment is 2-4.
4. The process of claim 1 wherein the gas is a gas of a cobalt production processThe method for recycling the body is characterized in that the current density of the electrolytic deposition method in the step (7) is 300-400A/m 2 The cell voltage is 2-3V.
5. The method for recycling gas in the cobalt production process according to claim 1, wherein the cobalt carbonate calcined in the step (8) in the hydrogen atmosphere is calcined at 400-600 ℃ for 3-5h.
6. The method for recycling gas in the cobalt production process according to claim 1, wherein in the step (1), a heat exchanger 1 is arranged outside the roasting furnace, high-temperature smoke dust and gas generated in the roasting process are replaced by low-temperature smoke dust and gas, the low-temperature smoke dust and gas comprise smoke dust, sulfur trioxide, sulfur dioxide and water vapor, the smoke dust is collected through cyclone, cloth bag and electric dust collection, the sulfur trioxide and the sulfur dioxide are subjected to catalytic oxidation, and the water vapor is used for preparing sulfuric acid; and (3) replacing the low-temperature reuse water with high-temperature reuse water by the heat exchanger 1 for water leaching treatment in the step (2), wherein the water leaching treatment is carried out in a reaction kettle with a coil pipe device.
7. The method for recycling gas generated in the cobalt production process according to claim 6, wherein the sulfuric acid prepared from sulfur trioxide, sulfur dioxide and water vapor is purified and used for cobalt washing in the loaded organic phase 1 and back extraction of the loaded organic phase 2 in the step (4) and roasting in the step (1).
8. The method for recycling gas generated in the cobalt production process according to claim 1, wherein the chlorine gas generated in the electrolytic deposition process in the step (7) is used for leaching oxidation impurity removal.
9. The method for recycling steam in the cobalt production process according to claim 1, wherein the byproduct hydrogen in the step (7) is collected and then used for preparing cobalt powder by calcining cobalt carbonate in the step (8).
10. The method for recycling steam in the cobalt production process according to claim 1, wherein a heat exchanger 2 is arranged outside the calcining furnace in the step (8), the high-temperature carbon dioxide gas generated after the cobalt carbonate is calcined is replaced by low-temperature carbon dioxide gas through the heat exchanger 2, and then the high-temperature carbon dioxide gas reacts with ammonia water to prepare ammonium bicarbonate, the low-temperature ammonium chloride solution is replaced by a high-temperature ammonium chloride solution through the heat exchanger 2 to promote the decomposition of ammonium chloride crystals to generate ammonia gas, hydrogen chloride and water vapor, the ammonia gas is used for the alkali-adding saponification of the organic-poor phase 1 in the step (4) and the alkali-adding saponification of the organic-poor phase 2 in the step (6) and the preparation of ammonium bicarbonate, the hydrogen chloride is dissolved in water to prepare a hydrochloric acid solution for the back extraction of the cobalt-containing organic phase in the step (6), the water vapor is used for preparing sulfuric acid, and the solvent water in the ammonium chloride solution is used as the recycle water in the water immersion step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435631.7A CN115747478B (en) | 2022-11-16 | 2022-11-16 | Method for realizing gas recycling in cobalt production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435631.7A CN115747478B (en) | 2022-11-16 | 2022-11-16 | Method for realizing gas recycling in cobalt production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115747478A true CN115747478A (en) | 2023-03-07 |
| CN115747478B CN115747478B (en) | 2023-07-07 |
Family
ID=85372071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211435631.7A Active CN115747478B (en) | 2022-11-16 | 2022-11-16 | Method for realizing gas recycling in cobalt production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115747478B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB357366A (en) * | 1929-09-17 | 1931-09-24 | Eugen Assar Alexis Groenwall | Process for the recovery of cobalt or compounds thereof |
| JPS50112211A (en) * | 1974-02-13 | 1975-09-03 | ||
| US4594102A (en) * | 1983-03-29 | 1986-06-10 | Sherritt Gordon Mines Limited | Recovery of cobalt and nickel from sulphidic material |
| CN100999782A (en) * | 2006-11-27 | 2007-07-18 | 紫金矿业集团股份有限公司 | Comprehensive recovering process of multimetal sulfide mineral |
| CN101250626A (en) * | 2008-03-18 | 2008-08-27 | 贵研铂业股份有限公司 | Method for extracting metallic nickel cobalt from irony nickel mine |
| CN109234522A (en) * | 2018-09-28 | 2019-01-18 | 浙江科菲科技股份有限公司 | A kind of cobalt iron concentrate synthetical recovery processing method |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
-
2022
- 2022-11-16 CN CN202211435631.7A patent/CN115747478B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB357366A (en) * | 1929-09-17 | 1931-09-24 | Eugen Assar Alexis Groenwall | Process for the recovery of cobalt or compounds thereof |
| JPS50112211A (en) * | 1974-02-13 | 1975-09-03 | ||
| US4594102A (en) * | 1983-03-29 | 1986-06-10 | Sherritt Gordon Mines Limited | Recovery of cobalt and nickel from sulphidic material |
| CN100999782A (en) * | 2006-11-27 | 2007-07-18 | 紫金矿业集团股份有限公司 | Comprehensive recovering process of multimetal sulfide mineral |
| CN101250626A (en) * | 2008-03-18 | 2008-08-27 | 贵研铂业股份有限公司 | Method for extracting metallic nickel cobalt from irony nickel mine |
| CN109234522A (en) * | 2018-09-28 | 2019-01-18 | 浙江科菲科技股份有限公司 | A kind of cobalt iron concentrate synthetical recovery processing method |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
Non-Patent Citations (1)
| Title |
|---|
| 何文龙;兰玮锋;吴世发;: "含钴黄铁矿硫酸化焙烧浸出研究", 中国资源综合利用, no. 06, pages 221 - 222 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115747478B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107017443B (en) | A method for comprehensive recovery of valuable metals from waste lithium-ion batteries | |
| CN108550939B (en) | A method for selectively reclaiming lithium and preparing lithium carbonate from waste lithium batteries | |
| CN108149015B (en) | Method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching | |
| CN107017444A (en) | A kind of method of metal recovery in waste lithium iron phosphate battery | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN113666437B (en) | Method for preparing nickel sulfate from nickel-iron-copper alloy | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN106611841B (en) | A method for preparing nickel-cobalt-manganese ternary material precursor by utilizing nickel-cobalt slag material | |
| CN112226630B (en) | Method for extracting valuable metal elements from laterite-nickel ore by hydrochloric acid leaching method and acid-base regeneration circulation | |
| CN102534223A (en) | Method for recovering valuable metals from spent lithium-ion batteries | |
| CN102676803B (en) | Resource utilization method for catalytic oxidation leaching of molybdenum and nickel from molybdenum-nickel ore | |
| CN114132909A (en) | Method for recycling pure metal salt from retired manganese iron phosphate lithium battery waste | |
| CN115074540B (en) | Comprehensive recovery method for valuable components of waste power battery | |
| CN113511664A (en) | Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste | |
| CN107046154B (en) | Method for enhanced reduction leaching of waste ternary lithium battery | |
| CN112522512B (en) | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| CN101250622B (en) | Complete wet way comprehensive processing method for serpentine mine | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| CN100516252C (en) | A method for processing copper oxide ore | |
| CN115571925B (en) | Method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries | |
| CN112652807A (en) | Method for selectively recovering lithium in anode material of waste lithium ion battery by using Lewis acid | |
| CN113846219B (en) | Method for extracting lithium from waste lithium batteries | |
| CN117512342B (en) | Method for recycling lithium from waste ternary lithium ion battery anode material | |
| CN118792520A (en) | A method for recovering metal in positive electrode by using calcium sulfate sulfidation roasting | |
| CN115747478B (en) | Method for realizing gas recycling in cobalt production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |