CN113387387A - Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process - Google Patents
Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process Download PDFInfo
- Publication number
- CN113387387A CN113387387A CN202110885932.9A CN202110885932A CN113387387A CN 113387387 A CN113387387 A CN 113387387A CN 202110885932 A CN202110885932 A CN 202110885932A CN 113387387 A CN113387387 A CN 113387387A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- containing waste
- waste
- tungstate solution
- sodium tungstate
- 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.)
- Pending
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 123
- 239000010937 tungsten Substances 0.000 title claims abstract description 123
- 239000002699 waste material Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 72
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002386 leaching Methods 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000011268 mixed slurry Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000004927 fusion Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000002791 soaking Methods 0.000 description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940045872 sodium percarbonate Drugs 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 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 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 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
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for preparing sodium tungstate solution from tungsten-containing waste by using an alkali fusion roasting-water leaching method, which comprises the following steps: s1, directly and uniformly mixing the tungsten-containing waste with alkali, and then roasting to obtain a roasted product; s2, carrying out water leaching on the roasted product to obtain a solid-liquid mixture, and filtering the solid-liquid mixture to obtain filter residue and leachate; s3, adjusting the pH value of the leachate to 9-11 to obtain mixed slurry, and filtering to obtain a sodium tungstate solution. The sodium tungstate solution can be directly evaporated and crystallized to obtain a sodium tungstate product, and can also be subjected to an ion exchange process or an extraction process to obtain an ammonium tungstate solution, and the ammonium tungstate solution is evaporated and crystallized to obtain an APT product. The method provided by the invention is suitable for recycling various tungsten-containing wastes, and the tungsten-containing waste treatment method has the advantages of short process flow and high metal recovery rate, is a green and efficient treatment method, and has great popularization and application values.
Description
Technical Field
The invention relates to a method for producing sodium tungstate solution by using tungsten-containing waste, which is a novel technology for treating tungsten-containing waste by a short-flow process and belongs to the field of industrial solid waste treatment.
Background
The development of modern industry has led to an increasing amount of scrap cemented carbide called "industrial teeth". With the gradual exhaustion of strategic primary tungsten ore resources, how to comprehensively recover valuable metals from tungsten-containing waste secondary resources has become a research subject of great attention at home and abroad. The literature reports that: about 2.7 million tons of metal tungsten is consumed in China every year, and the hard alloy accounts for more than 50 percent of tungsten application products. The tungsten-containing waste mainly comprises two main types of powder and lump materials according to physical specifications. The tungsten-containing waste materials generally contain tungsten carbide, tungsten, cobalt and a small amount of impurities such as iron, chromium, copper, silicon and the like; tungsten and cobalt are extremely important strategic metals, and the regeneration and recovery of tungsten and cobalt from tungsten-containing waste is extremely valuable work and has great significance for relieving the problem of strategic resource shortage of tungsten and cobalt.
At present, the technical method for treating the tungsten-containing waste at home and abroad mainly comprises a saltpeter smelting method, a zinc smelting method, an oxidizing roasting-alkaline leaching method, an electrochemical method, a high-temperature oxidizing roasting-reducing method, a mechanical crushing method, an acid leaching method and a sodium sulfate melting method, the first step of the technological scheme for recycling the tungsten-containing waste is also the most critical step, the hard phase WC and the binder phase metal Co are separated by a physical method or a chemical method, and then the tungsten and the cobalt are respectively extracted and the products are prepared.
CN109022763A discloses a method for treating tungsten-containing waste and a device thereof, wherein the method comprises the following steps: granulating the tungsten-containing waste to obtain granular tungsten-containing waste; roasting the granular tungsten-containing waste obtained in the step 1 to obtain a roasted material; adding the additive into the roasted material obtained in the step 2 while the additive is hot, and reacting by using the residual temperature after roasting to obtain a melt; and (4) carrying out water leaching on the melt obtained in the step (3) to obtain a solution and a solid. The equipment comprises granulation equipment, roasting equipment, dust collecting equipment, a water immersion tank, a material pumping pump, solid-liquid separation equipment, concentration equipment, drying equipment and packaging equipment. Although the method adopts sodium carbonate, sodium hydroxide and sodium percarbonate as roasting additives, the tungsten-containing waste can also be used for preparing sodium tungstate solution; however, the first step of the process comprises a granulation pretreatment process of the tungsten-containing waste, the particle size of the tungsten-containing waste is required, and a sodium percarbonate reagent is additionally added to be used as an oxidant in the roasting process, so that the process has the technical characteristics of long process flow and high production cost.
In view of the problems in the existing process for recovering sodium tungstate from tungsten-containing waste, a short-flow, efficient, clean and low-cost tungsten-containing waste treatment method is urgently needed to achieve the purpose of efficiently utilizing solid waste resources.
Disclosure of Invention
The invention aims to provide a method for producing sodium tungstate solution by utilizing a short-process technology of tungsten-containing waste, and reduce the impurity content of the sodium tungstate solution.
In order to achieve the aim, the invention provides a method for preparing sodium tungstate solution by utilizing tungsten-containing waste materials in a short process, which comprises the following steps: s1, uniformly mixing the tungsten-containing waste with alkali, and then roasting to obtain a roasted product; s2, carrying out water leaching on the roasted product to obtain a solid-liquid mixture, and filtering the solid-liquid mixture to obtain filter residue and leachate; s3, adjusting the pH value of the leachate to 9-11 to obtain mixed slurry, and filtering to obtain a sodium tungstate solution.
Further, the step S1 includes: fully mixing tungsten-containing waste with alkali to obtain a mixture; and roasting the mixture at 500-1200 ℃ for 0.5-3 hours to obtain a roasted product.
Further, the tungsten-containing waste material obtained in step S1 is derived from a flooring material, a dust collecting material, a grinding material, and a waste material generated in the production process of cemented carbide, a powdery tungsten-containing waste material such as a flooring material, a dust collecting material, and a waste material generated in the production process of tungsten carbide powder and tungsten powder, and further includes a massive tungsten-containing waste material such as waste tungsten steel, waste drill bits, waste cutters, waste molds, and waste tungsten rods. The tungsten-containing waste material mainly comprises the following components: the mass content of tungsten is 40-95%, the mass content of cobalt is 2-20%, and simultaneously, the tungsten powder also contains a small amount of other impurity elements such as Fe, Cu, C, Cr, SiO2, Ni, V and the like.
Further, the alkali in the step S1 is a solid alkali and/or a liquid alkali, and is preferably at least one selected from sodium hydroxide, sodium carbonate, and sodium bicarbonate.
Further, the mass of the alkali in the step S1 is 1 to 4 times of the mass of the tungsten-containing waste. When the alkali is sodium hydroxide, the mass ratio of the tungsten waste to the sodium hydroxide is 1: (1-3); when the alkali is sodium carbonate, the mass ratio of the tungsten waste to the sodium carbonate is 1: (1-3); when the alkali is sodium carbonate, the mass ratio of the tungsten waste to the sodium carbonate is 1: (2-4); when the alkali is a mixture of sodium hydroxide, sodium carbonate and sodium bicarbonate, the mass ratio of the tungsten waste to the sodium hydroxide to the sodium carbonate to the sodium bicarbonate is 1: (0.5-1.5): (0.5-2): (0.5 to 1.5).
Further, the roasting temperature is 500-1200 ℃, the heating rate is 2.5-10 ℃/min, and the heat preservation time is 0.5-3 hours.
Further, the step S2 includes: after the temperature of the roasted material melt is reduced to room temperature, adding water into the roasted material to soak for 2-6 hours to form slurry, wherein the weight ratio of the water to the roasted material in the slurry is 2-8: 1; and stirring the slurry to carry out water leaching, wherein the water leaching process lasts for 0.5-2 h, the temperature of the slurry is maintained at 20-80 ℃, water leaching is carried out to obtain a solid-liquid mixture, and the solid-liquid mixture is filtered to obtain filter residue and a leaching solution.
Further, in the step S3, inorganic acid or water is added to adjust the pH of the leachate to 9-11, so as to obtain a mixed slurry, and the mixed slurry is filtered to obtain a sodium tungstate solution.
Further, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
Further, the step S3 includes heating the leachate to 60 to 100 ℃ and maintaining the temperature for 10 to 30 minutes before filtering the mixed slurry.
Further, the mixed slurry is filtered to obtain a sodium tungstate solution.
Further, evaporating and crystallizing the sodium tungstate solution to obtain a sodium tungstate product, or extracting or carrying out an ion exchange process on the sodium tungstate solution to obtain an ammonium tungstate solution, and evaporating and crystallizing the ammonium tungstate solution to obtain an APT product.
The invention also protects the product obtained by the treatment method of the tungsten-containing waste material, which comprises at least one of sodium tungstate solution, sodium tungstate product and APT product.
The invention has the following beneficial effects:
the treatment method is suitable for common tungsten-containing waste materials, and comprises a floor material, a dust collecting material, a grinding material and a waste material which are generated in the production process of hard alloy, a floor material, a dust collecting material and a waste material which are generated in the production process of tungsten carbide powder and tungsten powder, and also comprises blocky hard waste materials such as waste tungsten steel, waste drill bits, waste cutters, waste molds, waste tungsten rods and the like. Furthermore, the first step in the technical scheme involved in CN109022763A includes a granulation pretreatment process of the tungsten-containing waste, and after intensive research, the inventors of the present invention found that the blocky tungsten-containing waste such as waste tools, waste tungsten steels, waste drill bits, waste molds, waste tungsten rods, etc. is roasted at a high temperature of 1000 ℃, the blocky tungsten-containing waste is gradually cracked from the surface to the center direction along with the prolongation of the roasting time, and the high-temperature alkali-molten state of alkali roasting aggravates the erosion cracking speed of the blocky tungsten-containing waste, so that the present invention can directly treat the powdery tungsten-containing waste and the blocky tungsten-containing waste, and even if the blocky waste hard alloy material is treated, the pretreatment processes such as crushing, granulation, etc. are not needed, the process flow is shortened, and the production cost is saved; furthermore, the invention directly adopts the common alkali as the roasting additive, thereby not only avoiding the problem of gas pollution in the sodium sulfate melting process, but also not needing to add sodium peroxide, sodium nitrate, and oxidants such as sodium percarbonate and the like described in CN109022763A, and reducing the medicament cost; furthermore, the method effectively removes Cr, Cu, Fe and SiO contained in the crude sodium tungstate solution by adjusting the dosage and the type of alkali, the roasting parameters and the pH value of the water leaching solution 2And the quality of the sodium tungstate solution is improved by waiting for impurities, and tungsten content in the obtained solution is detected and analyzedThe recovery rate of (D) is over 98%. In a word, the tungsten-containing waste material treatment method has the advantages of short process flow, high metal recovery rate and good raw material adaptability, and is an environment-friendly treatment method.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a schematic diagram of a process flow for producing a sodium tungstate solution from tungsten-containing waste in accordance with an exemplary embodiment of the present invention;
fig. 2 shows a schematic process flow diagram of the process for producing APT from tungsten-containing waste material according to a preferred embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to solve the technical problems of long process flow, complex separation method, low recovery rate, easy generation of gas pollution and the like in the process of producing sodium tungstate solution by using tungsten-containing waste grinding materials in the prior art, the invention provides a method for producing sodium tungstate solution by using tungsten-containing waste materials, and according to an embodiment of the invention, with reference to the attached drawing 1, the method comprises the following steps:
S1: the tungsten-containing waste is uniformly mixed with alkali and then roasted to obtain a roasted product.
In the embodiment of the invention, in order to ensure that tungsten in the tungsten-containing waste material is fully reacted with alkali to generate sodium tungstate to be separated, the leaching rate of tungsten is greatly improved, so that the total yield of tungsten is improved, and for the powdery tungsten-containing waste material, the mass of alkali in the step S1 is preferably 1-2 times of that of the tungsten-containing waste material; in order to increase the chance of contact between the alkali and the bulk tungsten-containing waste material due to the chemical reaction, the amount of the alkali used is increased, and the mass of the alkali in step S1 is preferably 2 to 4 times the mass of the bulk tungsten-containing waste material. In addition, while ensuring the efficient alkali-melting conversion effect of the tungsten componentOn the premise that the lower the usage amount of the alkali, the better, the consumption cost of the alkali can be reduced, and the Cr and SiO in the subsequent water leaching solution can be reduced2The content of (a).
In the embodiment of the present invention, the specific values of the baking temperature and the baking time are not particularly limited, and those skilled in the art can optionally select the values according to actual needs, and as a preferred scheme, the baking temperature is 500 to 1200 ℃, and the baking time is 0.5 to 3 hours. In the roasting temperature and roasting time range, the oxidation roasting and alkali conversion of tungsten components in the tungsten-containing waste are more thorough. It should be added that, raising the roasting temperature and prolonging the roasting time can both improve the copper and iron removal effect, i.e. reduce the contents of Cu and Fe in the subsequent water leaching solution. In addition, it should be noted that the roasting system contains oxidizing gas, and the roasting is performed in air, which is known to those skilled in the art and will not be described herein. It should be added that the alkali fusion roasting-water leaching method of adding oxidants such as sodium peroxide, sodium nitrate, sodium percarbonate and the like is adopted, so that more Cr components in the tungsten-containing waste material easily enter the water leaching solution.
S2: and (3) carrying out water leaching on the roasted product to obtain a solid-liquid mixture, and filtering the solid-liquid mixture to obtain filter residue and a leaching solution.
In the embodiment, the weight ratio of water to the roasted material is controlled within the range of 2-8: 1, and the roasted material is soaked for 2-6 hours, so that the problem that the roasted material melt is bonded with a crucible can be effectively solved, soluble substances in the roasted material can be fully dissolved in water, sodium tungstate in the roasted material is further completely dissolved out, and the leaching rate of the sodium tungstate is further ensured. Meanwhile, the roasted material obtained after roasting is higher in temperature and higher in activity, so that the leaching effect is better when the roasting is carried out in water, in the embodiment, the temperature of the slurry is maintained between 20 ℃ and 80 ℃ in the water leaching process, and the water leaching time is 0.5-2 h. The apparatus for filtering the solid-liquid mixture is not particularly limited as long as it can separate the solid phase from the liquid phase.
S3: and adjusting the pH value of the leaching solution to 9-11 to obtain mixed slurry, and filtering to obtain a sodium tungstate solution.
After the leachate is obtained, in order to improve the purity of the sodium tungstate, the pH of the leachate is preferably adjusted to 9 to 11 by using a mineral acid in step S3. Under the pH value, trace impurities such as chromium, arsenic and silicon are efficiently removed in a positive and negative charge adsorption synergistic coprecipitation mode, the precipitates are further filtered, impurities such as chromium, arsenic and silicon in the sodium tungstate solution can be effectively removed, the purity of the sodium tungstate solution is improved, and the subsequent preparation of qualified tungsten products is facilitated. Inorganic acids useful in the present invention include, but are not limited to, one or more of hydrochloric acid, sulfuric acid, phosphoric acid.
In another preferred embodiment of the present invention, the step S3 includes heating the leachate to 60 to 90 ℃ and maintaining the temperature for 10 to 30 minutes before filtering the mixed slurry. The heating aims to ensure that the chromium, arsenic, silicon and other ions are completely co-precipitated, and the precipitated particles are large and convenient to filter, so that the leachate is purified.
The purified sodium tungstate solution can be directly evaporated, concentrated and crystallized to obtain a high-purity sodium tungstate product, or an ion exchange-evaporative crystallization process shown in figure 2 can be adopted to produce a high-quality ammonium paratungstate product, or the sodium tungstate solution is subjected to an extraction-evaporative crystallization process to obtain an ammonium paratungstate product.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 30g of blocky tungsten-containing waste, adding sodium hydroxide with the mass ratio of 2 times into the tungsten-containing waste, and uniformly mixing to obtain a mixture; roasting the mixture at the roasting temperature of 900 ℃ for 1h to obtain a roasted material;
Step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 6:1 to the roasted material to soak for 3 hours to obtain slurry, stirring the slurry to soak for 1 hour at the water soaking temperature of 60 ℃, and filtering to obtain filter residue and leachate after water soaking;
step three: and (4) adding hydrochloric acid into the leachate obtained in the step two to adjust the pH value of the leachate to 10, stirring, heating to 80 ℃, preserving heat for 10 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten is up to 98.6%, Cr, Cu, Fe and SiO2The leaching rates of (A) were 1.2%, 0.8%, 0.6%, and 1.3%, respectively.
Example 2: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 40g of powdery tungsten-containing waste, adding sodium bicarbonate with the mass ratio of 1.5 times into the tungsten-containing waste, and uniformly mixing to obtain a mixture; roasting the mixture at the roasting temperature of 600 ℃ for 2h to obtain a roasted material;
step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 4:1 to the roasted material for soaking for 4 hours to obtain slurry, stirring the slurry for soaking for 1 hour at the water soaking temperature of 80 ℃, and filtering to obtain filter residue and leachate;
step three: and (4) adding sulfuric acid into the leachate obtained in the step two to adjust the pH value of the leachate to 9, stirring, heating to 90 ℃, preserving heat for 20 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten reaches 99.2 percent, and Cr, Cu, Fe and SiO 2The leaching rates of (A) were 1.1%, 0.7%, 0.5%, and 0.9%, respectively.
Example 3: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 50g of powdery tungsten-containing waste, adding 2 times of sodium carbonate into the tungsten-containing waste, and uniformly mixing to obtain a mixture; roasting the mixture at 800 ℃ for 1h to obtain a roasted material;
step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 2:1 to the roasted material to soak for 6 hours to obtain slurry, stirring the slurry to soak for 2 hours at the water soaking temperature of 60 ℃, and filtering to obtain filter residue and leachate after water soaking;
step three: adding phosphoric acid into the leachate obtained in the second step to adjust the pH value of the leachateAnd (4) stirring, heating to 95 ℃, preserving the heat for 20 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten is up to 97.5%, Cr, Cu, Fe and SiO2The leaching rates of (A) were 1.5%, 1.1%, 0.8% and 1.2%, respectively.
Example 4: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 30g of blocky tungsten-containing waste, adding sodium carbonate with the mass ratio of 4 times into the tungsten-containing waste, and uniformly mixing to obtain a mixture; roasting the mixture at 1200 ℃ for 1h to obtain a roasted material;
Step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 8:1 to the roasted material to soak for 2 hours to obtain slurry, stirring the slurry to soak for 1 hour at the water soaking temperature of 80 ℃, and filtering to obtain filter residue and leachate after water soaking;
step three: and (4) adding sulfuric acid into the leachate obtained in the step two to adjust the pH value of the leachate to 11, stirring, heating to 80 ℃, keeping the temperature for 20 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten is up to 98.2%, Cr, Cu, Fe and SiO2The leaching rates of (A) were 1.5%, 0.6%, 0.3%, and 1.4%, respectively.
Example 5: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 40g of powdery tungsten-containing waste, adding 1 time of sodium carbonate and 0.5 time of sodium bicarbonate into the tungsten-containing waste respectively in mass ratio, and uniformly mixing to obtain a mixture; roasting the mixture at 500 ℃ for 3h to obtain a roasted material;
step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 6:1 to the roasted material to soak for 3 hours to obtain slurry, stirring the slurry to soak for 1 hour at the water soaking temperature of 60 ℃, and filtering to obtain filter residue and leachate after water soaking;
step three: and (4) adding phosphoric acid into the leachate obtained in the step two to adjust the pH value of the leachate to 10, stirring, heating to 95 ℃, keeping the temperature for 20 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten is up to 98.6%, Cr, Cu, Fe and SiO 2The leaching rates of (A) were 1.3%, 1.1% and 0, respectively.9％、1.2％。
Example 6: the method for producing the sodium tungstate solution by using the tungsten-containing waste comprises the following steps:
the method comprises the following steps: taking 60g of blocky tungsten-containing waste, adding 1 time of sodium hydroxide and 1 time of sodium bicarbonate into the tungsten-containing waste respectively in mass ratio, and uniformly mixing to obtain a mixture; roasting the mixture at 1000 ℃ for 2h to obtain a roasted material;
step two: after the roasted material is cooled to room temperature, adding water with the weight ratio of 3:1 to the roasted material to soak for 4 hours to obtain slurry, stirring the slurry to soak for 0.5 hour at the water soaking temperature of 20 ℃, and filtering to obtain filter residue and leachate;
step three: and (4) adding hydrochloric acid into the leachate obtained in the step two to adjust the pH value of the leachate to 11, stirring, heating to 60 ℃, preserving heat for 30 minutes, and filtering to obtain a sodium tungstate solution. The recovery rate of tungsten reaches 99.6 percent, and Cr, Cu, Fe and SiO2The leaching rates of (A) were 0.9%, 0.5%, 0.3%, and 0.7%, respectively.
Comparative example 1
Other conditions are not changed, the mass ratio of the sodium hydroxide addition amount to the massive tungsten scraps is changed to be 0.5 times in example 1, the final tungsten recovery rate is only 46.8 percent, and the Cr, Cu, Fe and SiO are added2The leaching rates of (A) were 0.5%, 0.4%, 0.3%, and 0.7%, respectively.
Comparative example 2
The final recovery rate of tungsten was only 99.7% by changing the amount of sodium hydroxide added to the bulk tungsten scrap in example 1 to 5 times the mass ratio with the other conditions being unchanged, but the final recovery rate of Cr, Cu, Fe, SiO2The leaching rates are respectively 25.8 percent, 1.2 percent, 0.9 percent and 36.9 percent, namely under the premise of ensuring the high-efficiency alkali-melting conversion effect of the tungsten component, the more the alkali is used, the more Cr and SiO are in the sodium tungstate solution2The impurity content is obviously improved.
Comparative example 3
The other conditions are not changed, the roasting temperature and the roasting time in the example 2 are respectively changed into 400 ℃ and 0.3h, the final recovery rate of the tungsten is only 67.3 percent, and the Cr, Cu, Fe and SiO2The leaching rates of (A) and (B) were 1.4%, 5.1%, 6.2% and 0.7%, respectively, that isThe roasting temperature is reduced, the roasting time is shortened, the recovery rate of tungsten is obviously reduced, and the leaching rates of Cu and Fe are higher than 5%, so that the impurity contents of Cu and Fe in the sodium tungstate solution are higher.
Comparative example 4
Under the same conditions, sodium carbonate with the mass ratio of 2 times that of the tungsten-containing waste material in example 3 was added, and sodium peroxide, sodium nitrate and sodium percarbonate with the mass ratio of 0.2 time that of the tungsten-containing waste material were added, respectively, so that the recovery rate of tungsten was 98.1%, but the leaching rates of Cr were 7.4%, 11.8% and 5.3%, respectively, i.e., the content of Cr in the sodium tungstate solution was relatively high.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (10)
1. A method for preparing sodium tungstate solution by utilizing tungsten-containing waste in a short process is characterized by comprising the following steps of:
s1, uniformly mixing the tungsten-containing waste with alkali, and then roasting to obtain a roasted product;
s2, carrying out water leaching on the roasted product to obtain a solid-liquid mixture, and filtering the solid-liquid mixture to obtain filter residue and leachate;
s3, adjusting the pH value of the leachate to 9-11 to obtain mixed slurry, and filtering to obtain a sodium tungstate solution.
2. The method of claim 1, wherein: the tungsten-containing waste is derived from floor materials, dust collecting materials, grinding materials and waste materials generated in the production process of hard alloy, powdery tungsten-containing waste materials such as floor materials, dust collecting materials and waste materials in the production process of tungsten carbide powder and tungsten powder, and also comprises blocky tungsten-containing waste materials such as waste tungsten steel, waste drill bits, waste cutters, waste molds and waste tungsten rods, wherein the tungsten-containing waste materials mainly comprise the following components: 40-95% of tungsten by mass, 2-20% of cobalt by mass, and a small amount of Fe, Cu、C、Cr、SiO2And other impurity elements such as Ni and V.
3. The method of claim 1, wherein: the alkali is solid alkali and/or liquid alkali, preferably at least one selected from sodium hydroxide, sodium carbonate and sodium bicarbonate.
4. The method of claim 1, wherein: and in the step S1, the mass of the alkali is 1-4 times of that of the tungsten-containing waste.
5. The method of claim 1, wherein: the roasting temperature is 500-1200 ℃, and the roasting time is 0.5-3 hours.
6. The method of claim 1, wherein: the step S2 includes:
after the temperature of the roasted material melt is reduced to room temperature, adding water into the roasted material to soak for 2-6 hours to form slurry, wherein the weight ratio of the water to the roasted material in the slurry is 2-8: 1; and stirring the slurry to carry out water leaching, wherein the water leaching process lasts for 0.5-2 h, the temperature of the slurry is maintained at 20-80 ℃, water leaching is carried out to obtain a solid-liquid mixture, and the solid-liquid mixture is filtered to obtain filter residue and a leaching solution.
7. The method of claim 1, wherein: and in the step S3, adding inorganic acid or water to adjust the pH value of the leachate to 9-11, and then filtering to obtain a sodium tungstate solution.
8. The method of claim 7, wherein: the inorganic acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
9. The method of claim 1, wherein: in the step S3, the method includes the step of heating the leachate to 60 to 100 ℃ and preserving the temperature for 10 to 30 minutes before filtering the mixed slurry.
10. The method of claim 1, wherein: and (2) evaporating and crystallizing the sodium tungstate solution to obtain a sodium tungstate product, or extracting or ion exchanging the solution containing sodium tungstate to obtain an ammonium tungstate solution, and evaporating and crystallizing the ammonium tungstate solution to obtain an APT product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110885932.9A CN113387387A (en) | 2021-08-03 | 2021-08-03 | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110885932.9A CN113387387A (en) | 2021-08-03 | 2021-08-03 | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113387387A true CN113387387A (en) | 2021-09-14 |
Family
ID=77622304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110885932.9A Pending CN113387387A (en) | 2021-08-03 | 2021-08-03 | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113387387A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114873645A (en) * | 2022-06-08 | 2022-08-09 | 赣州海盛钨业股份有限公司 | Method for preparing sodium tungstate by recycling tungsten waste |
| CN114921649B (en) * | 2022-03-22 | 2023-11-10 | 湖北绿钨资源循环有限公司 | Method for recycling soluble tungstate in tungsten-containing waste |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950984A (en) * | 2014-04-23 | 2014-07-30 | 湖南顺泰钨业股份有限公司 | Method for producing sodium tungstate solution by use of tungsten-containing waste grinding material, and sodium tungstate |
| CN104603306A (en) * | 2012-09-07 | 2015-05-06 | 韩国地质资源研究院 | Method for leaching valuable metals contained in waste denitrification catalyst by using roasting and water leaching |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
| CN108751259A (en) * | 2018-08-17 | 2018-11-06 | 厦门钨业股份有限公司 | A kind of method and its device of tungsten waste production ammonium metatungstate |
| CN108975406A (en) * | 2018-08-17 | 2018-12-11 | 厦门钨业股份有限公司 | A kind of method and device thereof of tungsten waste production APT |
| CN109022763A (en) * | 2018-08-17 | 2018-12-18 | 厦门钨业股份有限公司 | A kind of processing method and its equipment of tungsten waste |
| CN110055402A (en) * | 2019-05-29 | 2019-07-26 | 厦门钨业股份有限公司 | A kind of processing method and processing unit of tungsten waste material |
| CN110878390A (en) * | 2019-11-13 | 2020-03-13 | 厦门钨业股份有限公司 | Method for recovering tungsten from waste hard alloy |
-
2021
- 2021-08-03 CN CN202110885932.9A patent/CN113387387A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104603306A (en) * | 2012-09-07 | 2015-05-06 | 韩国地质资源研究院 | Method for leaching valuable metals contained in waste denitrification catalyst by using roasting and water leaching |
| CN103950984A (en) * | 2014-04-23 | 2014-07-30 | 湖南顺泰钨业股份有限公司 | Method for producing sodium tungstate solution by use of tungsten-containing waste grinding material, and sodium tungstate |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
| CN108751259A (en) * | 2018-08-17 | 2018-11-06 | 厦门钨业股份有限公司 | A kind of method and its device of tungsten waste production ammonium metatungstate |
| CN108975406A (en) * | 2018-08-17 | 2018-12-11 | 厦门钨业股份有限公司 | A kind of method and device thereof of tungsten waste production APT |
| CN109022763A (en) * | 2018-08-17 | 2018-12-18 | 厦门钨业股份有限公司 | A kind of processing method and its equipment of tungsten waste |
| CN110055402A (en) * | 2019-05-29 | 2019-07-26 | 厦门钨业股份有限公司 | A kind of processing method and processing unit of tungsten waste material |
| CN110878390A (en) * | 2019-11-13 | 2020-03-13 | 厦门钨业股份有限公司 | Method for recovering tungsten from waste hard alloy |
Non-Patent Citations (2)
| Title |
|---|
| 吴永谦等: "从某高温合金酸浸渣中回收钨的研究", 《矿冶工程》 * |
| 郭超等: "硬质合金磨削废料中钨的回收利用研究", 《中国钨业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114921649B (en) * | 2022-03-22 | 2023-11-10 | 湖北绿钨资源循环有限公司 | Method for recycling soluble tungstate in tungsten-containing waste |
| CN114873645A (en) * | 2022-06-08 | 2022-08-09 | 赣州海盛钨业股份有限公司 | Method for preparing sodium tungstate by recycling tungsten waste |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108751259B (en) | Method and device for producing ammonium metatungstate by tungsten-containing waste | |
| CN102560100B (en) | Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy | |
| CN109022763B (en) | Treatment method and equipment for tungsten-containing waste | |
| CN103950984B (en) | The tungstenic grinding material that gives up is utilized to produce the method for sodium tungstate solution and sodium wolframate | |
| CN104498718A (en) | Method for treating hard alloy grinding material | |
| CN108975406B (en) | Method and device for producing APT (ammonium paratungstate) by using tungsten-containing waste | |
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN103088207A (en) | Efficient vanadium extraction method by performing alkali roasting on vanadium mineral | |
| CN113387387A (en) | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process | |
| CN115140777B (en) | Method for producing ferromanganese composite material for soft magnetic by utilizing ocean manganese nodule | |
| CN101831542B (en) | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings | |
| CN102923764A (en) | Method for preparing sodium stannate from stannic oxide and sodium salt in reduction roasting manner | |
| CN110747330A (en) | Method for preparing chloridizable titanium-rich material by reducing ilmenite | |
| CN112941312A (en) | Comprehensive recovery process for antimony and arsenic smelting alkaline residue | |
| CN105543490A (en) | Method for preparing ZnO from blast furnace gas ash through microwave roasting pretreatment and ammonia leaching | |
| CN104762483B (en) | A kind of method that copper bismuth slag produces copper sulphate | |
| CN113060765A (en) | Oxygen-enriched decomposition process of tungsten raw material | |
| CN111074076B (en) | Comprehensive utilization system and method for metallurgical solid waste | |
| CN111057837B (en) | Low-temperature roasting treatment method for cobalt hydrometallurgy waste residues | |
| KR102228192B1 (en) | Preparing method of nickel-cobalt-manganese complex sulphate solution by recycling wasted electrode material | |
| CN104445105B (en) | Method for enriching and recovering tellurium dioxide from tellurium-containing soda residue | |
| CN101824539A (en) | Wet metallurgy method for decomposing hard alloy | |
| CN114317979A (en) | Method for recovering aluminum from ionic rare earth impurity removal slag | |
| CN113061755A (en) | Process for producing ammonium paratungstate by flotation type tungsten raw material oxygen-enriched leaching full-wet method | |
| CN116654988B (en) | Method for preparing battery grade manganous-manganic oxide by using manganese-containing waste residues |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210914 |
|
| RJ01 | Rejection of invention patent application after publication |