CN115744991B - Method for preparing tungsten oxide from tungsten-containing waste - Google Patents
Method for preparing tungsten oxide from tungsten-containing waste Download PDFInfo
- Publication number
- CN115744991B CN115744991B CN202211481563.8A CN202211481563A CN115744991B CN 115744991 B CN115744991 B CN 115744991B CN 202211481563 A CN202211481563 A CN 202211481563A CN 115744991 B CN115744991 B CN 115744991B
- Authority
- CN
- China
- Prior art keywords
- tungsten
- containing waste
- leaching
- preparing
- roasting
- 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.)
- Active
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 110
- 239000010937 tungsten Substances 0.000 title claims abstract description 110
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 76
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 58
- 238000002386 leaching Methods 0.000 claims abstract description 119
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002893 slag Substances 0.000 claims abstract description 40
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000011268 mixed slurry Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007790 solid phase Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 230000001180 sulfating effect Effects 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 9
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 239000012071 phase Substances 0.000 abstract description 17
- 238000007654 immersion Methods 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- GSTANBWEAXRNHP-UHFFFAOYSA-N azanium;hydrogen carbonate;sodium Chemical compound [NH4+].[Na].OC([O-])=O GSTANBWEAXRNHP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing tungsten oxide from tungsten-containing waste. The method comprises the following steps: and (3) carrying out sulfating roasting on the mixed slurry of the tungsten-containing waste and sulfuric acid, roasting, carrying out calcine stirring water leaching, carrying out solid-liquid separation after water leaching to obtain tungstic acid solid-phase slag and cobalt salt solution, and calcining the tungstic acid solid-phase slag to obtain tungsten oxide. The method of the invention utilizes the strong oxidizing property and acid solubility of high-concentration sulfuric acid in the roasting process to convert tungsten-containing phases such as tungsten carbide, tungsten and the like in tungsten-containing waste into insoluble tungstic acid, and non-tungsten components such as cobalt, iron and the like into soluble sulfate, and can realize the high-efficiency separation of tungsten and other components by water immersion; and the tungsten oxide can be prepared by a short-flow process, so that the energy consumption and the production cost are greatly reduced, the operation is simple and convenient, the efficiency is high, and the industrial popularization and application prospect is good.
Description
Technical Field
One or more embodiments of the present disclosure relate to the field of recycling tungsten-containing waste materials, and in particular, to a method for preparing tungsten oxide from tungsten-containing waste materials.
Background
In order to make up for the shortage of the original tungsten ore resources, the research on the industrial problem of recycling the tungsten-containing waste is urgent. At present, more than 50% of tungsten resources worldwide are used for manufacturing hard alloy, the tungsten content in waste hard alloy reaches 74% -91%, the tungsten metal is consumed in China for about 2.7 ten thousand t each year, and if the recovery rate can reach 40%, the method has great significance in establishing a resource guarantee system and promoting the development of circular economy.
The existing recovery treatment method of tungsten-containing waste at home and abroad mainly comprises the following steps: zinc smelting, saltpeter smelting, roasting alkaline leaching, electrochemical process, in-situ oxidation-reduction carbonization process, etc. these resource recycling techniques have certain advantages and disadvantages. The zinc melting method has the advantages of wide application range, maturity, short flow and tungsten recovery rate up to 95%; but the method is only suitable for processing hard alloy with cobalt content lower than 10%, has high electricity consumption, high requirement on zinc vapor recovery equipment and large zinc volatilization pollution; in addition, the zinc melting method is easy to introduce impurities, has low recovery rate and is not suitable for treating powder waste. The nitrate melting method has the advantages of early application, wide application, low investment, easy leaching of products and high reaction speed, but has the defects of long industrial process, expensive and high consumption of raw and auxiliary materials, high production cost and pollution of discharged tail gas to the environment. The roasting alkaline leaching method is to convert tungsten waste into tungsten oxide through oxidation roasting, and the tungsten oxide generates sodium tungstate through alkaline leaching reaction, so that the purpose of recycling tungsten is achieved, however, the roasting equipment of the method has serious furnace formation, high tungsten content in slag, low recovery rate and high secondary slag treatment cost; and the waste water generated later is more, and the loss of raw and auxiliary materials is large. The electrochemical method is only suitable for treating waste hard alloy with Co content of more than 8% (mass fraction), namely the treatment range is limited. The in-situ oxidation-reduction carbonization method has the problems of insufficient powder purity, substandard alloy performance and the like. The method mainly realizes the separation of components such as tungsten carbide and cobalt in a binding phase in tungsten-containing waste, or further obtains a crude sodium tungstate solution, and the obtained tungsten carbide or crude sodium tungstate solution can be used for preparing tungsten oxide only by a plurality of complex procedures.
The tungsten oxide is used as an industrial primary raw material and can be used for producing tungsten smelting products such as ammonium paratungstate and tungsten powder, and at present, in the recycling process for treating tungsten-containing waste, the transformation of tungsten carbide and/or tungsten in the tungsten-containing waste into tungsten oxide is a necessary process. At present, the tungsten oxide is prepared by treating tungsten-containing waste by acid leaching cobalt and then oxidizing roasting, for example, patent CN106673064A discloses a method for producing ammonium paratungstate by treating hard alloy grinding materials, which comprises the following steps: firstly, adding water into a hard alloy grinding material to prepare slurry, and pumping the slurry into a reaction kettle to carry out acid leaching treatment to realize tungsten-cobalt separation; carrying out high-temperature (600-1000 ℃) oxidizing roasting on the obtained tungsten carbide slag for 3-10 hours to obtain a tungsten oxide material, carrying out alkaline leaching treatment on the tungsten oxide material to obtain a crude sodium tungstate solution, and carrying out traditional procedures such as ion exchange, evaporative crystallization and the like to obtain an ammonium paratungstate product; the process has the defects of high energy consumption, long process flow, high treatment cost and the like. CN102808086a discloses a method for preparing superfine tungsten oxide nano powder by recovering waste hard alloy through hydrothermal method, which comprises the steps of cleaning waste hard alloy, placing into autoclave, adding energyFluoride capable of providing fluoride ions, adding concentrated nitric acid and hydrogen peroxide to oxidize tungsten carbide in the hard alloy completely, and treating the reaction kettle at the constant temperature of 120-200 ℃ for 6-48 hours; cooling the reaction kettle, separating solid phase from liquid phase, drying solid phase, and pulverizing with mortar to obtain superfine WO 3 A nano powder; the method needs expensive equipment such as an autoclave, and the like, has high equipment operation requirement, long process flow and high cost. CN 108439473A discloses a method for preparing nano tungsten oxide from waste hard alloy containing tungsten, which comprises the steps of leaching powdery waste material containing tungsten with sodium hydroxide in a stainless steel reaction kettle at high temperature and high pressure, adding sulfuric acid solution into alkaline solution containing tungsten to adjust pH, controlling pH to 3-5, and keeping the solution clear all the time; adding TOA and N235 combined extractant and sodium bicarbonate ammonium to the solution for extraction and back extraction, and then heating, evaporating, crystallizing, drying and calcining again to obtain nano tungsten oxide; the method has long process flow, high reagent consumption, high equipment operation requirement and difficult wastewater treatment.
In summary, the existing treatment method for preparing tungsten oxide from tungsten-containing waste generally has the defects of long process flow, high equipment requirement, high energy consumption, high treatment cost and the like, so that development of a novel method for preparing tungsten oxide from tungsten-containing waste is urgently needed to solve the problems.
Disclosure of Invention
The present invention aims to solve the problems set forth in the background art, and one or more embodiments of the present invention aim to provide a method for preparing tungsten oxide from tungsten-containing waste, which is a regeneration treatment method for tungsten-containing waste with short flow, high efficiency and low cost.
In view of the above, one or more embodiments of the present specification provide a method for preparing tungsten oxide from tungsten-containing waste, including the steps of:
s1, preparing mixed slurry: uniformly stirring and mixing tungsten-containing waste and sulfuric acid to obtain mixed slurry;
s2, sulfating roasting: placing the mixed slurry obtained in the step S1 into roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting to obtain calcine for later use;
s3, soaking in water: stirring and leaching the calcine obtained in the step S2 by using water, and carrying out solid-liquid separation after water leaching, wherein leaching residues are tungstic acid solid-phase residues, and leaching liquid is cobalt salt solution;
s4, calcining: calcining the tungstic acid solid-phase slag obtained in the step S3 at a preset temperature for a certain time to obtain a tungsten oxide product.
Preferably, the tungsten-containing waste material in the step S1 is bulk waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with the particle size of 1-3 mm; floor material, dust collection material, grinding material and waste material generated in the hard alloy production process; tungsten carbide powder, powdery tungsten-containing waste in floor materials, dust collecting materials and waste materials in the tungsten powder production process; the tungsten-containing waste comprises the following components:
tungsten, 40% -95% by mass;
cobalt accounting for 2 to 20 percent of the total mass; and
other impurities.
Preferably, the mass ratio of the tungsten-containing waste to sulfuric acid in the step S1 is 1: mixing evenly according to the proportion of 0.2-1; the mass percentage concentration of the sulfuric acid is more than 70%.
Preferably, the baking temperature in the step S2 is 200-500 ℃.
Preferably, the roasting time in the step S2 is 1-5h.
Preferably, the roasting atmosphere in the step S2 is an oxidizing atmosphere, and may be one or more of air, oxygen-enriched air or oxygen.
Preferably, the acidified tail gas generated in the sulfating roasting process in the step S2 is recycled after being washed by an acid washing circulation absorption system.
Preferably, the water immersion temperature of the calcine water immersion process in the step S3 is 20-80 ℃, and the liquid-solid ratio is 3-10: 1mL/g, and leaching time is 0.5-3h.
Preferably, the stirring speed in the water leaching process in the step S3 is 100-600r/min.
Preferably, the cobalt salt solution in the step S3 may be purified by chemical precipitation to remove impurities, and then the cobalt oxalate product is prepared by using ammonium oxalate to precipitate cobalt or the cobalt oxalate product is calcined to produce and prepare the cobalt oxide powder product.
Preferably, the calcination temperature of the tungstic acid solid-phase slag in the step S4 is 500-800 ℃.
Preferably, the calcination time of the tungstic acid solid-phase slag in the step S4 is 1-6h.
Preferably, the tungstic acid solid-phase slag in the step S3 can be directly calcined to prepare a tungsten oxide product; or dissolving the tungstic acid solid slag into ammonium tungstate solution by ammonia water, and preparing an ammonium paratungstate product after evaporating and crystallizing; the solid-phase slag of the tungstic acid can be dissolved into a sodium tungstate solution by alkaline leaching, and then the ammonium tungstate solution is obtained by an ion exchange process or an extraction process, and the ammonium paratungstate product is obtained by evaporating and crystallizing the ammonium tungstate solution.
The advantageous effects of the present invention are described in detail below with reference to the embodiments of the present invention and the accompanying drawings.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a schematic process flow diagram of the method of the present invention.
FIG. 2 shows XRD analysis results of the leaching residue obtained in example 1 of the present invention.
FIG. 3 is the XRD analysis of the tungsten oxide product obtained in example 1 of the present invention.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples.
Referring to fig. 1-3, a method for preparing tungsten oxide from tungsten-containing waste material includes the following steps:
s1, preparing mixed slurry: and uniformly stirring and mixing the tungsten-containing waste and sulfuric acid to obtain mixed slurry. Optionally, the tungsten-containing waste material in the step S1 is bulk waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with the particle size of 1-3 mm; floor material, dust collection material, grinding material and waste material generated in the hard alloy production process; tungsten carbide powder, powdery tungsten-containing waste in floor materials, dust collecting materials and waste materials in the tungsten powder production process; the tungsten-containing waste comprises the following components: tungsten, 40% -95% by mass; cobalt accounting for 2 to 20 percent of the total mass; and other impurities. Optionally, the other impurities are one or more of Fe, cu, C, cr, siO, ni and V. Optionally, the tungsten-containing waste and sulfuric acid are mixed according to a mass ratio of 1: mixing evenly in a proportion of 0.2-1. Optionally, the mass percentage concentration of the sulfuric acid is more than 70%.
S2, sulfating roasting: placing the mixed slurry obtained in the step S1 into roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting to obtain calcine for standby, wherein the main chemical reaction equation in the process is as follows: WC+Co+H 2 SO 4 +3O 2(g) ＝H 2 WO 4 +CoSO 4 +CO 2 (g)；W+Co+H 2 SO 4 +2O 2(g) ＝H 2 WO 4 +CoSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The technical principle is as follows: the tungsten-containing waste is sulfated and roasted, tungsten carbide, tungsten and other tungsten-containing phases in the tungsten-containing waste are converted into tungstic acid by utilizing the strong oxidizing property and acid solubility of high-concentration sulfuric acid in the sulfating and roasting process, cobalt, iron and other non-tungsten components are converted into soluble sulfate, tungsten is insoluble in water by utilizing the tungstic acid, and the tungsten can be effectively separated from other components such as cobalt, iron and the like by water immersion. Optionally, the roasting equipment in the step S2 is tubular resistance furnace, muffle furnace, reverberatory furnace, rotary kiln, multi-hearth furnace or fluidized bed roasting equipment in the current industrial production, and the production mode can be continuous production or intermittent production. Optionally, the baking temperature is 200-500 ℃. Optionally, the roasting time is 1-5h. Optionally, the roasting atmosphere is an oxidizing atmosphere, and may be one or more of air, oxygen-enriched air or oxygen. Optionally, the acidified tail gas generated in the sulfation roasting process is absorbed by acid washing circulationAnd (3) recycling the system after washing, and using the sulfuric acid as a sulfuric acid material in the step S1.
S3, soaking in water: stirring and leaching the calcine obtained in the step S2 by using water, and carrying out solid-liquid separation after water leaching, wherein leaching residues are tungstic acid solid-phase residues, and leaching liquid is cobalt salt solution. Optionally, the water immersion temperature is 20-80 ℃, and the liquid-solid ratio is 3-10: 1mL/g, and leaching time is 0.5-3h. Optionally, the stirring speed is 100-600r/min. Optionally, the cobalt salt solution can be purified and decontaminated by a chemical precipitation method, and then the cobalt oxalate product is prepared by using ammonium oxalate to precipitate cobalt or the cobalt oxalate product is produced and prepared by calcining cobalt oxalate.
S4, calcining: calcining the tungstic acid solid-phase slag obtained in the step S3 at a preset temperature for a certain time to produce a tungsten oxide product, wherein the chemical equation of the main reaction in the process is H 2 WO 4 ＝WO 3 +H 2 O (g) . Optionally, the calcination temperature of the tungstic acid solid-phase slag is 500-800 ℃. Optionally, the calcination time of the tungstic acid solid-phase slag is 1-6h.
In the embodiment of the invention, the tungsten acid solid-phase slag can be directly calcined to prepare a tungsten oxide product; or dissolving the tungstic acid solid slag into ammonium tungstate solution by ammonia water, and preparing an ammonium paratungstate product after evaporating and crystallizing; the solid-phase slag of the tungstic acid can be dissolved into a sodium tungstate solution by alkaline leaching, and then the ammonium tungstate solution is obtained by an ion exchange process or an extraction process, and the ammonium paratungstate product is obtained by evaporating and crystallizing the ammonium tungstate solution.
Example 1
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 50g of sulfuric acid solution with mass concentration of 90% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 2 hours; stirring and leaching the calcine at 80 ℃, wherein the liquid-solid ratio is 7:1mL/g, and leaching time is 2h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag are shown in figure 2, and the fact that the leaching slag is mainly a tungstic acid phase is proved; and the Co leaching rate is 99.58% after analysis and detection;
step 3: the leaching residue was calcined at 800 ℃ for 1h to prepare a tungsten oxide product (XRD analysis result is shown in FIG. 3), and XRD analysis proves that the leaching residue is completely converted into WO after calcination 3 。
Comparative example 1
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 50g of sulfuric acid solution with mass concentration of 50% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 2 hours; stirring and leaching the calcine at 80 ℃, wherein the liquid-solid ratio is 7:1mL/g, and leaching time is 2h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results show that the leaching slag is mainly WC phase; and the leaching rate of Co is 82.37 percent after analysis and detection; under the sulfating roasting condition that the concentration of sulfuric acid is low, the tungsten-containing waste is difficult to realize the oxidation conversion of tungsten carbide into tungstic acid, and only part of Co can be separated from the tungsten carbide.
Step 3: calcining the leaching residue at 800 deg.C for 1 hr, and XRD analysis shows that the main phase of the calcined product is WC, and only a small amount of WO 3 And (5) generating.
Example 2
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% respectively and 70g of sulfuric acid solution with mass concentration of 90% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 400 ℃ for 4 hours; the calcine is stirred and immersed at 60 ℃, the liquid-solid ratio is 10:1mL/g, and the immersion time is 1h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the leaching rate of Co is 98.51 percent after analysis and detection;
step 3: will beThe leaching residue was calcined at 700 ℃ for 3 hours to prepare a tungsten oxide product. XRD analysis proves that the leaching residue can be completely converted into WO 3 。
Comparative example 2
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% respectively and 70g of sulfuric acid solution with mass concentration of 90% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at the temperature of 100 ℃ for 4 hours; the calcine is stirred and immersed at 60 ℃, the liquid-solid ratio is 10:1mL/g, and the immersion time is 1h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of leaching slag show that the leaching slag is mainly tungsten carbide phase, and Co leaching rate is 75.62% after analysis and detection; namely, the sulfating roasting is carried out under the condition of lower temperature, the directional conversion of tungsten carbide into tungstic acid is difficult to realize, and the Co leaching rate is lower under the condition of low-temperature roasting.
Step 3: the leaching residue was calcined at 700 ℃ for 3 hours to prepare a tungsten oxide product. The main phase of the calcined product was still WC, only small amounts of WO, as analyzed by XRD 3 And (5) generating.
Example 3
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 100g of sulfuric acid solution with mass concentration of 70% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 400 ℃ for 5 hours; stirring and leaching the calcine at 20 ℃ for 1h at a liquid-solid ratio of 5:1 mL/g; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the Co leaching rate is 99.39% after analysis and detection;
step 3: the leaching residue was calcined at 600 ℃ for 2 hours to prepare a tungsten oxide product. XRD analysis proves that the leaching residue energyComplete conversion to WO 3 。
Comparative example 3
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 100g of sulfuric acid solution with mass concentration of 70% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 700 ℃ for 5 hours; stirring and leaching the calcine at 20 ℃ for 1h at a liquid-solid ratio of 5:1 mL/g; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of leaching residues prove that the leaching residues mainly comprise tungstic acid and cobalt tungstate phases; and the leaching rate of Co is 65.13 percent after analysis and detection; namely, under the sulfating roasting condition that the roasting temperature is too high, part of cobalt phase is converted into cobalt tungstate which is difficult to dissolve in water, so that the Co leaching rate is reduced.
Step 3: the leaching residue was calcined at 600 ℃ for 2 hours to prepare a tungsten oxide product. The phase of the leaching residue is mainly WO by XRD analysis 3 And CoO.
Example 4
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% respectively and 20g of sulfuric acid solution with the mass concentration of 98% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 3 hours; the calcine is stirred and immersed at 50 ℃ with a liquid-solid ratio of 8:1mL/g for 2h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the leaching rate of Co is 97.23 percent after analysis and detection;
step 3: the leaching residue was calcined at 800 ℃ for 1 hour to prepare a tungsten oxide product. XRD analysis shows that the leaching residue is completely converted into WO after calcination 3 。
Example 5
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 50g of sulfuric acid solution with mass concentration of 80% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 1h; the temperature of the calcine stirred water immersion is 80 ℃, the liquid-solid ratio is 3:1mL/g, and the water immersion time is 0.5h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the Co leaching rate is 98.27% after analysis and detection;
step 3: the leaching residue was calcined at 800 ℃ for 1 hour to prepare a tungsten oxide product. XRD analysis shows that the leaching residue is completely converted into WO after calcination 3 。
Example 6
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% respectively and 80g of sulfuric acid solution with mass concentration of 80% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 2 hours; stirring and leaching the calcine at 20 ℃ for 3h at a liquid-solid ratio of 5:1 mL/g; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the Co leaching rate is 99.14% after analysis and detection;
step 3: the leaching residue was calcined at 600 ℃ for 6 hours to prepare a tungsten oxide product. XRD analysis shows that the leaching residue is completely converted into WO after calcination 3 。
Example 7
The method for preparing tungsten oxide by sulfating roasting-water leaching-roasting tungsten-containing waste comprises the following steps:
step 1: 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% respectively and 60g of sulfuric acid solution with mass concentration of 90% are stirred and mixed uniformly to obtain mixed slurry;
step 2: roasting the mixed slurry at 300 ℃ for 5 hours; the calcine is stirred and immersed at 60 ℃, the liquid-solid ratio is 7:1mL/g, and the immersion time is 2h; leaching residues and leaching liquid are obtained through solid-liquid separation after water leaching. XRD analysis results of the leaching slag prove that the leaching slag is mainly a tungstic acid phase; and the Co leaching rate is 99.67% after analysis and detection;
step 3: the leaching residue was calcined at 500 ℃ for 5 hours to prepare a tungsten oxide product. XRD analysis shows that the leaching residue is completely converted into WO after calcination 3 。
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (11)
1. A method for preparing tungsten oxide from tungsten-containing waste, which is characterized by comprising the following steps:
s1, preparing mixed slurry: uniformly stirring and mixing tungsten-containing waste and sulfuric acid to obtain mixed slurry;
s2, sulfating roasting: placing the mixed slurry obtained in the step S1 into roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting to obtain calcine for later use;
s3, soaking in water: stirring and leaching the calcine obtained in the step S2 by using water, and carrying out solid-liquid separation after water leaching, wherein leaching residues are tungstic acid solid-phase residues, and leaching liquid is cobalt salt solution;
s4, calcining: calcining the tungstic acid solid-phase slag obtained in the step S3 at a preset temperature for a certain time to obtain a tungsten oxide product;
wherein the tungsten-containing waste material in the step S1 is bulk waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with the particle size of 1-3 mm; floor material, dust collection material, grinding material and waste material generated in the hard alloy production process; tungsten carbide powder, powdery tungsten-containing waste in floor materials, dust collecting materials and waste materials in the tungsten powder production process; the tungsten-containing waste comprises the following components:
tungsten, 40% -95% by mass;
cobalt, 2% -20% by mass; and
other impurities;
wherein, the tungsten-containing waste material and sulfuric acid in the step S1 are mixed according to the mass ratio of 1: mixing evenly according to the proportion of 0.2-1; the mass percentage concentration of the sulfuric acid is more than 70%.
2. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the firing temperature in the step S2 is 200 to 500 ℃.
3. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the firing time in the step S2 is 1 to 5 hours.
4. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the roasting atmosphere in the step S2 is an oxidizing atmosphere, and is one or a combination of more of air, oxygen-enriched air and oxygen.
5. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the acidified tail gas generated in the sulfating roasting process in the step S2 is recycled after being washed by an acid washing circulation absorption system.
6. The method for preparing tungsten oxide by using the tungsten-containing waste material according to claim 1, wherein the water leaching temperature of the calcine water leaching process in the step S3 is 20-80 ℃, and the liquid-solid ratio is 3-10: 1mL/g, and leaching time is 0.5-3h.
7. The method for preparing tungsten oxide by using the tungsten-containing waste material according to claim 1, wherein the stirring speed in the water leaching process in the step S3 is 100-600r/min.
8. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the cobalt salt solution in step S3 is purified by chemical precipitation method to remove impurities, and then cobalt oxalate product is prepared by using ammonium oxalate to precipitate cobalt or cobalt oxalate is calcined to produce cobalt oxide powder product.
9. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the tungsten acid solid-phase slag calcining temperature in the step S4 is 500-800 ℃.
10. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the tungsten acid solid-phase slag calcination time in the step S4 is 1-6h.
11. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the tungsten acid solid-phase slag of step S3 is directly calcined to prepare tungsten oxide product; or dissolving the tungstic acid solid-phase slag into ammonium tungstate solution by using ammonia water, and preparing an ammonium paratungstate product after evaporating and crystallizing; or the solid-phase slag of the tungstic acid is dissolved into a sodium tungstate solution by utilizing alkaline leaching, then an ammonium tungstate solution is obtained by utilizing an ion exchange process or an extraction process, and an ammonium paratungstate product is obtained by evaporating and crystallizing the ammonium tungstate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211481563.8A CN115744991B (en) | 2022-11-24 | 2022-11-24 | Method for preparing tungsten oxide from tungsten-containing waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211481563.8A CN115744991B (en) | 2022-11-24 | 2022-11-24 | Method for preparing tungsten oxide from tungsten-containing waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115744991A CN115744991A (en) | 2023-03-07 |
| CN115744991B true CN115744991B (en) | 2023-12-26 |
Family
ID=85336941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211481563.8A Active CN115744991B (en) | 2022-11-24 | 2022-11-24 | Method for preparing tungsten oxide from tungsten-containing waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115744991B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201245459A (en) * | 2011-05-06 | 2012-11-16 | Hong Jing Metal Corp | Method for recycling metal from tungsten-containing waste catalysis |
| CN103436704A (en) * | 2013-09-11 | 2013-12-11 | 北京化工大学 | Method for recovering vanadium and tungsten from tungsten containing vanadium-titanium based waste denitration catalyst |
| CN103526052A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Method for recovering tungsten from tungsten-containing fluorite ore |
| CN110156084A (en) * | 2019-06-04 | 2019-08-23 | 赣州市海龙钨钼有限公司 | A kind of process using waste hand alloy material production ammonium paratungstate |
| CN110714124A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste recovery slag |
| CN114934169A (en) * | 2022-05-13 | 2022-08-23 | 中南大学 | Method for recycling tungsten-containing waste |
-
2022
- 2022-11-24 CN CN202211481563.8A patent/CN115744991B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201245459A (en) * | 2011-05-06 | 2012-11-16 | Hong Jing Metal Corp | Method for recycling metal from tungsten-containing waste catalysis |
| CN103436704A (en) * | 2013-09-11 | 2013-12-11 | 北京化工大学 | Method for recovering vanadium and tungsten from tungsten containing vanadium-titanium based waste denitration catalyst |
| CN103526052A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Method for recovering tungsten from tungsten-containing fluorite ore |
| CN110156084A (en) * | 2019-06-04 | 2019-08-23 | 赣州市海龙钨钼有限公司 | A kind of process using waste hand alloy material production ammonium paratungstate |
| CN110714124A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste recovery slag |
| CN114934169A (en) * | 2022-05-13 | 2022-08-23 | 中南大学 | Method for recycling tungsten-containing waste |
Non-Patent Citations (1)
| Title |
|---|
| 从钨渣中浸出氧化钪的试验研究;梁焕龙;罗东明;刘晨;谢营邦;黄泰元;;湿法冶金(第02期);第114-116页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115744991A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108751259B (en) | Method and device for producing ammonium metatungstate by tungsten-containing waste | |
| CN106848473B (en) | Method for selectively recovering lithium in waste lithium iron phosphate batteries | |
| CN110066920B (en) | Method for selectively leaching and separating vanadium and iron from stone coal vanadium ore | |
| CN109897962B (en) | Method and device for recovering tungsten in tungsten-containing waste by adopting oxidation smelting method | |
| WO2012171481A1 (en) | Hydrometallurgical process for complete and comprehensive recovery with substantially no wastes and zero emissions | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN110643815B (en) | Recycling harmless treatment method for black copper mud | |
| CN106929696A (en) | TiCl4Refine method of the tailings ammonium soak for high-purity vanadium oxide | |
| CN114684801B (en) | Method for preparing high-purity ferric phosphate by using pyrite cinder | |
| CN106048251A (en) | Technological method for cleaning and efficiently treating arsenic matte | |
| CN109706312A (en) | A method of vanadic anhydride and chemical electrode manganese dioxide are prepared simultaneously using vanadium chromium slag and low-grade pyrolusite | |
| CN114058851A (en) | Method for recycling tungsten, molybdenum and titanium from waste denitration catalyst | |
| CN113637840A (en) | Method for recovering zinc from zinc ferrite resource by using calcification ball-milling roasting-alkaline leaching method | |
| CN111254276A (en) | Method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of sodium reduction roasting | |
| CN110735032B (en) | Vanadium-titanium-iron paragenetic ore treatment process | |
| CN115074540A (en) | Comprehensive recovery method for valuable components of waste power battery | |
| CN113862464B (en) | Method for recovering copper and scattered metal in black copper sludge | |
| CN113149075A (en) | Method for preparing niobium pentoxide from low-grade niobium ore | |
| CN111534699A (en) | Method for recovering valuable substances from cemented carbide scrap | |
| CN115744991B (en) | Method for preparing tungsten oxide from tungsten-containing waste | |
| CN110760683A (en) | Method for extracting vanadium from waste SCR catalyst and preparing alkali metal fluotitanate, product and application thereof | |
| CN114934169B (en) | Method for recycling tungsten-containing waste | |
| CN113976129B (en) | Method for preparing manganese carbonate and iron-based SCR catalyst by using manganese tailings and copperas | |
| CN114959309A (en) | Method for forcibly leaching vanadium from vanadium titano-magnetite | |
| CN110629043B (en) | Bismuth extraction method based on phase transformation of bismuth sulfide ore |
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 |