CN115744991A - Method for preparing tungsten oxide from tungsten-containing waste - Google Patents
Method for preparing tungsten oxide from tungsten-containing waste Download PDFInfo
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- CN115744991A CN115744991A CN202211481563.8A CN202211481563A CN115744991A CN 115744991 A CN115744991 A CN 115744991A CN 202211481563 A CN202211481563 A CN 202211481563A CN 115744991 A CN115744991 A CN 115744991A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 108
- 239000010937 tungsten Substances 0.000 title claims abstract description 108
- 239000002699 waste material Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 82
- 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 60
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 60
- 238000002386 leaching Methods 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 39
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000011268 mixed slurry Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 28
- 239000007790 solid phase Substances 0.000 claims abstract description 25
- 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
- 230000001180 sulfating effect Effects 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 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 12
- 238000007654 immersion Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- 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
- 239000004576 sand Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 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
- 238000000227 grinding Methods 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
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 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
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 17
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect 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
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000007547 defect Effects 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
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003513 alkali 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution 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
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping 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
- 238000006467 substitution reaction Methods 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
Images
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
Abstract
The invention discloses a method for preparing tungsten oxide from tungsten-containing waste. The method comprises the following steps: and (2) carrying out sulfating roasting on the mixed slurry of the tungsten-containing waste and sulfuric acid, stirring and water leaching the roasted product after roasting, carrying out solid-liquid separation after water leaching to obtain tungstic acid solid-phase slag and a cobalt salt solution, and calcining the tungstic acid solid-phase slag to obtain tungsten oxide. According to the method, tungsten-containing phases such as tungsten carbide and tungsten in the tungsten-containing waste are converted into insoluble tungstic acid by utilizing strong oxidizability and acid solubility of high-concentration sulfuric acid in the roasting process, non-tungsten components such as cobalt and iron are converted into soluble sulfate, and the tungsten can be efficiently separated from 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 technical field of recycling tungsten-containing waste, and in particular, to a method for preparing tungsten oxide from tungsten-containing waste.
Background
In order to make up for the shortage of the raw tungsten ore resources, the research on the industrial problem of recycling tungsten-containing waste is urgent. At present, more than 50% of tungsten resources are globally used for manufacturing hard alloys, while the tungsten content in waste hard alloys reaches 74% -91%, tungsten metal is consumed by China for about 2.7 ten thousand tons every year, and if the recovery rate can reach 40%, the method has great significance for establishing a resource guarantee system and promoting the development of circular economy.
At present, the existing tungsten-containing waste recycling and treating methods at home and abroad mainly comprise: the zinc melting method, the saltpeter melting method, the roasting alkaline leaching method, the electrochemical method, the in-situ oxidation-reduction carbonization method and the like have certain advantages and disadvantages in the resource recycling technology. The zinc melting method has the advantages of wide application, mature process, short flow, and tungsten recovery rate of 95%; but the method is only suitable for processing hard alloy with cobalt content lower than 10 percent, and has high power consumption, high requirement on zinc vapor recovery equipment and large zinc volatilization pollution; and the zinc melting method is easy to introduce impurities, has low recovery rate and is not suitable for treating powder waste. The saltpeter melting method has the advantages of early application, wide adaptability, low investment, easy leaching of products and high reaction speed, but has the defects of long industrial process, expensive and large loss of used raw and auxiliary materials, high production cost and environmental pollution caused by discharged tail gas. The roasting alkaline leaching method is to convert tungsten waste materials into tungsten oxide through oxidation roasting, and the tungsten oxide is subjected to alkaline leaching reaction to generate sodium tungstate, so that the purpose of tungsten recovery is achieved, however, roasting equipment in the method is serious in furnace formation, the tungsten content in slag is high, the recovery rate is low, and the secondary slag treatment cost is high; and the subsequent produced waste water is more, and the loss of the raw and auxiliary materials is large. The electrochemical method is only suitable for treating the waste hard alloy with the Co content of more than 8 percent (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 tungsten carbide, binder phase cobalt and other components in the tungsten-containing waste material, or further obtains a crude sodium tungstate solution, and the tungsten oxide can be prepared by subsequent treatment of the obtained tungsten carbide or crude sodium tungstate solution through a plurality of complex procedures.
Tungsten oxide is used as an industrial primary raw material and can be used for producing tungsten smelting products such as ammonium paratungstate, tungsten powder and the like, and currently, in the recycling process for treating tungsten-containing waste, the conversion of tungsten carbide andor tungsten in the tungsten-containing waste into tungsten oxide is a necessary procedure. Eyes of a userIn the former industry, tungsten oxide is prepared by treating tungsten-containing waste materials mainly through a process of acid leaching cobalt and oxidizing roasting, for example, patent CN106673064A discloses a method for treating hard alloy grinding materials to produce ammonium paratungstate, which comprises the following steps: firstly, adding water into a hard alloy grinding material for pulping, and then putting the hard alloy grinding material into a reaction kettle for 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 h to obtain a tungsten oxide material, carrying out alkaline leaching treatment on the tungsten oxide material to obtain a crude sodium tungstate solution, and then 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. CN 10280808086A discloses a method for preparing ultrafine tungsten oxide nano powder by recovering waste hard alloy by a hydrothermal method, which comprises the steps of cleaning the waste hard alloy, putting the cleaned waste hard alloy into a high-pressure kettle, adding fluoride capable of providing fluoride ions, adding concentrated nitric acid and hydrogen peroxide to completely oxidize tungsten carbide in the hard alloy, 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 the solid phase, and grinding with a mortar to obtain the superfine WO 3 A nanopowder; the method needs expensive equipment such as an autoclave and the like, has high equipment operation requirement, and has long process flow and high cost. CN 108439473A discloses a method for preparing nano tungsten oxide from tungsten-containing waste hard alloy, which comprises the steps of leaching powdery tungsten-containing waste materials in a stainless steel reaction kettle at high temperature and high pressure by using sodium hydroxide, adding a sulfuric acid solution into an alkali solution containing tungsten to adjust the pH value, controlling the pH value to be 3-5, and always keeping the solution clear; adding a combined extractant of TOA and N235 and sodium ammonium bicarbonate into the solution for extraction and back extraction, and then heating, evaporating, crystallizing, drying and calcining again to obtain nano tungsten oxide; the method has the advantages of 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 disadvantages of long process flow, high equipment requirement, high energy consumption, high treatment cost and the like, and therefore, the 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 is directed to solving the problems set forth in the background art, and an object of one or more embodiments of the present specification is to provide a method for preparing tungsten oxide from tungsten-containing waste, which is a regeneration treatment method of tungsten-containing waste having a short process, 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: stirring and mixing the tungsten-containing waste material and sulfuric acid uniformly to obtain mixed slurry;
s2, sulfating roasting: placing the mixed slurry obtained in the step S1 in roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting is finished to obtain roasted sand for later use;
s3, water immersion: stirring and leaching the calcine obtained in the step S2 with water, and performing solid-liquid separation after water leaching, wherein leaching residues are tungstic acid solid phase residues, and leaching solution is a cobalt salt solution;
s4, calcining: and (4) 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.
Preferably, the tungsten-containing waste material in the step S1 is a block waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with a particle size of 1-3 mm; floor material, dust collecting material, grinding material and waste material produced in the production process of hard alloy; tungsten carbide powder, and powdery tungsten-containing waste in floor materials, dust collecting materials and waste materials in the production process of tungsten powder; the tungsten-containing waste material comprises the following components:
tungsten, 40-95% by mass;
2-20% of cobalt by mass; and
other impurities.
Preferably, the tungsten-containing waste material and the sulfuric acid in the step S1 are mixed according to a mass ratio of 1: 0.2-1, mixing evenly; the mass percentage concentration of the sulfuric acid is more than 70%.
Preferably, the calcination temperature in the step S2 is 200 to 500 ℃.
Preferably, the roasting time in the step S2 is 1-5h.
Preferably, the roasting atmosphere in 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 washed by an acid washing circulating absorption system and then recycled.
Preferably, 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 the leaching time is 0.5-3h.
Preferably, the stirring speed in the water immersion process in the step S3 is 100-600r/min.
Preferably, the cobalt salt solution in step S3 may be purified by a chemical precipitation method to remove impurities, and then the cobalt oxalate product is prepared by precipitating cobalt with ammonium oxalate or the cobalt oxalate powder product is prepared by calcining cobalt oxalate.
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 to 6 hours.
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-phase residue into an ammonium tungstate solution by using ammonia water, and preparing an ammonium paratungstate product after evaporation and crystallization; or dissolving the tungstic acid solid-phase slag into sodium tungstate solution by using alkaline leaching, obtaining ammonium tungstate solution by using an ion exchange process or an extraction process, and obtaining an ammonium paratungstate product by evaporating and crystallizing the ammonium tungstate solution.
Advantageous effects of the present invention are described in detail below according to embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort from these drawings.
FIG. 1 is a schematic process flow diagram of the process of the present invention.
FIG. 2 shows the XRD analysis results of the leached out slag obtained in example 1 of the present invention.
FIG. 3 is the result of XRD analysis of the tungsten oxide product obtained in example 1 of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure will be described in further detail with reference to specific embodiments.
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 stirring and mixing the tungsten-containing waste material and sulfuric acid uniformly to obtain mixed slurry. Optionally, the tungsten-containing waste material in the step S1 is a block waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with a particle size of 1-3 mm; floor material, dust collecting material, grinding material and waste material produced in the production process of hard alloy; powdery tungsten-containing waste materials in floor materials, dust collecting materials and waste materials in the production process of tungsten carbide powder and tungsten powder; the tungsten-containing waste material comprises the following components: tungsten, 40-95% by mass; 2-20% of cobalt by mass; and other impurities. Optionally, the other impurities are one or more of Fe, cu, C, cr, siO2, ni, and V. Optionally, the tungsten-containing waste material and the sulfuric acid are mixed according to the mass ratio of 1: 0.2-1, and mixing uniformly. 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 in roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting is finished to obtain roasted sand for later use, wherein the formula of a main chemical reaction 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 (ii) a The technical principle is as follows: by sulfating roasting the tungsten-containing waste material, using sulfationIn the roasting process, tungsten-containing phases such as tungsten carbide and tungsten in the tungsten-containing waste are converted into tungstic acid along with the strong oxidability and acid solubility of high-concentration sulfuric acid, non-tungsten components such as cobalt and iron are converted into soluble sulfate, and the effective separation of tungsten from other components such as cobalt and iron can be realized by using the water insolubility of the tungstic acid and water immersion. Optionally, the roasting equipment in step S2 is a tubular resistance furnace, a muffle furnace, a reverberatory furnace, a rotary kiln, a multi-hearth furnace or a fluidized bed roasting equipment in the current industrial production, and the production mode may be continuous production or intermittent production. Optionally, the calcination temperature is 200-500 ℃. Optionally, the roasting time is 1-5h. Optionally, the roasting atmosphere is an oxidizing atmosphere, and may be one or a combination of more of air, oxygen-enriched air or oxygen. Optionally, the acidified tail gas generated in the sulfating roasting process is recycled after being washed by an acid washing circulating absorption system, and is used as the sulfuric acid material in the step S1.
S3, water immersion: and (3) stirring and leaching the calcine obtained in the step (2) by using water, and performing solid-liquid separation after water leaching, wherein leached residues are tungstic acid solid-phase residues, and a leaching solution is a cobalt salt solution. Optionally, the water immersion temperature is 20-80 ℃, and the liquid-solid ratio is 3-10: 1mL/g, and the leaching time is 0.5-3h. Optionally, the stirring speed is 100-600r/min. Optionally, the cobalt salt solution may be purified by a chemical precipitation method to remove impurities, and then the cobalt oxalate product is prepared by precipitating cobalt with ammonium oxalate or the cobalt oxalate product is calcined to prepare a cobalt oxide powder product.
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.
It should be noted that, in the embodiment of the present invention, the tungstic acid solid-phase slag can be directly calcined to prepare a tungsten oxide product; or dissolving the tungstic acid solid-phase slag into an ammonium tungstate solution by using ammonia water, and preparing an ammonium paratungstate product after evaporation and crystallization; or dissolving the tungstic acid solid-phase slag into a sodium tungstate solution by using alkaline leaching, obtaining an ammonium tungstate solution by using an ion exchange process or an extraction process, and obtaining an ammonium paratungstate product by evaporating and crystallizing the ammonium tungstate solution.
Example 1
The method for preparing tungsten oxide by sulfating roasting-water leaching-calcining tungsten-containing waste comprises the following steps:
step 1: uniformly stirring and mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 50g of 90% sulfuric acid solution to obtain mixed slurry;
and 2, step: roasting the mixed slurry at 500 ℃ for 2h; stirring and water leaching the calcine at the temperature of 80 ℃, with the liquid-solid ratio of 7; after water leaching, leaching residue and leachate are obtained through solid-liquid separation. XRD analysis results of the leaching residues are shown in figure 2, which proves that the leaching residues are mainly tungstic acid phases; and the Co leaching rate is 99.58% after analysis and detection;
and step 3: calcining the leaching residue at 800 deg.C for 1h to prepare tungsten oxide product (XRD analysis result is shown in figure 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 and calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 50g of 50% sulfuric acid solution to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 2h; stirring and water leaching the roasted sand at the temperature of 80 ℃, wherein the liquid-solid ratio is 7; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results show that the leaching slag is mainly a WC phase; and the Co leaching rate is 82.37% after analysis and detection; namely, under the sulfating roasting condition that the concentration of sulfuric acid is lower, the tungsten-containing waste material is difficult to realize the oxidation conversion of tungsten carbide into tungstic acid, and only part of Co can be separated from tungsten carbide.
And 3, step 3: calcining the leaching residue at 800 deg.C for 1h, and XRD analyzing to obtain the main phase of the calcined product which is WC with little amountAmount of WO 3 And (4) generating.
Example 2
The method for preparing tungsten oxide by sulfating roasting, water leaching and calcining tungsten-containing waste comprises the following steps:
step 1: uniformly stirring and mixing 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% and 70g of 90% sulfuric acid solution to obtain mixed slurry;
step 2: roasting the mixed slurry at 400 ℃ for 4h; stirring and water leaching the roasted sand at the temperature of 60 ℃, wherein the liquid-solid ratio is 10; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstic acid phases; and the Co leaching rate is 98.51% after analysis and detection;
and step 3: calcining the leaching residue at 700 ℃ for 3h to prepare a tungsten oxide product. XRD analysis proves that the leached residue can be completely converted into WO 3 。
Comparative example 2
The method for preparing tungsten oxide by sulfating roasting-water leaching-calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% and 70g of sulfuric acid solution with the mass concentration of 90% to obtain mixed slurry;
and 2, step: roasting the mixed slurry at 100 ℃ for 4 hours; stirring and water leaching the calcine at the temperature of 60 ℃, with the liquid-solid ratio of 10; after water leaching, leaching residue and leachate are obtained through solid-liquid separation. XRD analysis results of the leaching residues show that the leaching residues are mainly tungsten carbide phases, and the Co leaching rate obtained by analysis and detection is 75.62%; namely, sulfating roasting is carried out at a 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.
And step 3: calcining the leached slag at 700 ℃ for 3h to prepare a tungsten oxide product. The main phase of the calcined product is still WC by XRD analysis, and only a small amount of WO is contained 3 And (4) generating.
Example 3
The method for preparing tungsten oxide by sulfating roasting, water leaching and calcining tungsten-containing waste comprises the following steps:
step 1: uniformly stirring and mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 100g of sulfuric acid solution with mass concentration of 70% to obtain mixed slurry;
and 2, step: roasting the mixed slurry at 400 ℃ for 5 hours; stirring and water leaching the calcine at the temperature of 20 ℃, with the liquid-solid ratio of 5; after water leaching, leaching residue and leachate are obtained through solid-liquid separation. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstate phases; and the Co leaching rate is 99.39% after analysis and detection;
and step 3: calcining the leached slag at 600 ℃ for 2h to prepare a tungsten oxide product. XRD analysis proves that the leaching residue can be completely converted into WO 3 。
Comparative example 3
The method for preparing tungsten oxide by sulfating roasting, water leaching and calcining tungsten-containing waste comprises the following steps:
step 1: uniformly stirring and mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 100g of sulfuric acid solution with mass concentration of 70% to obtain mixed slurry;
and 2, step: roasting the mixed slurry at 700 ℃ for 5 hours; stirring and water leaching the roasted sand at the temperature of 20 ℃, wherein the liquid-solid ratio is 5; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstic acid and cobalt tungstate phases; and the Co leaching rate is 65.13% after analysis and detection; namely, under the sulfating roasting condition that the roasting temperature of the tungsten-containing waste is too high, partial cobalt phase is converted into cobalt tungstate which is difficult to dissolve in water, so that the Co leaching rate is reduced.
And step 3: calcining the leached slag at 600 ℃ for 2h 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-calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% and 20g of sulfuric acid solution with the mass concentration of 98% to obtain mixed slurry;
and 2, step: roasting the mixed slurry at 500 ℃ for 3h; stirring and water leaching the calcine at the temperature of 50 ℃, wherein the liquid-solid ratio is 8; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstic acid phases; and the Co leaching rate is 97.23% after analysis and detection;
and step 3: calcining the leached slag at 800 ℃ for 1h to prepare a tungsten oxide product. XRD analysis proves that the leaching residue is completely converted into WO after being calcined 3 。
Example 5
The method for preparing tungsten oxide by sulfating roasting, water leaching and calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 50g of sulfuric acid solution with mass concentration of 80% to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 1h; stirring and water leaching the roasted sand at the temperature of 80 ℃, wherein the liquid-solid ratio is 3; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstic acid phases; and the Co leaching rate is 98.27% after analysis and detection;
and step 3: calcining the leached slag at 800 ℃ for 1h to prepare a tungsten oxide product. XRD analysis proves that the leaching residue is completely converted into WO after being calcined 3 。
Example 6
The method for preparing tungsten oxide by sulfating roasting, water leaching and calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of granular tungsten-containing waste with tungsten and cobalt contents of 89wt.% and 10wt.% and 80g of sulfuric acid solution with the mass concentration of 80% to obtain mixed slurry;
step 2: roasting the mixed slurry at 500 ℃ for 2h; stirring and water leaching the roasted sand at the temperature of 20 ℃, wherein the liquid-solid ratio is 5; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstic acid phases; and the Co leaching rate is 99.14% after analysis and detection;
and 3, step 3: calcining the leaching residue at the temperature of 600 ℃ for 6 hours to prepare a tungsten oxide product. XRD analysis proves that the leaching residue is completely converted into WO after being calcined 3 。
Example 7
The method for preparing tungsten oxide by sulfating roasting-water leaching-calcining tungsten-containing waste comprises the following steps:
step 1: stirring and uniformly mixing 100g of powdery tungsten-containing waste with tungsten and cobalt contents of 85wt.% and 11wt.% and 60g of sulfuric acid solution with the mass concentration of 90% to obtain mixed slurry;
and 2, step: roasting the mixed slurry at the temperature of 300 ℃ for 5 hours; stirring and water leaching the roasted sand at the temperature of 60 ℃, wherein the liquid-solid ratio is 7; leaching residue and leachate are obtained by solid-liquid separation after water leaching. XRD analysis results of the leaching residues prove that the leaching residues are mainly tungstate phases; and the Co leaching rate is 99.67 percent after analysis and detection;
and 3, step 3: calcining the leaching residue at 500 ℃ for 5h to prepare a tungsten oxide product. XRD analysis proves that the leaching residue is completely converted into WO after being calcined 3 。
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (13)
1. The method for preparing tungsten oxide from tungsten-containing waste is characterized by comprising the following steps:
s1, preparing mixed slurry: stirring and mixing the tungsten-containing waste material and sulfuric acid uniformly to obtain mixed slurry;
s2, sulfating roasting: placing the mixed slurry obtained in the step S1 in roasting equipment, roasting for a preset time at a certain temperature, and slowly cooling to room temperature after roasting is finished to obtain roasted sand for later use;
s3, water immersion: stirring and leaching the calcine obtained in the step S2 with water, and performing solid-liquid separation after water leaching, wherein leaching residues are tungstic acid solid phase residues, and leaching solution is a cobalt salt solution;
s4, calcining: and (4) 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.
2. The method for preparing tungsten oxide from tungsten-containing waste material according to claim 1, wherein the tungsten-containing waste material in step S1 is bulk waste hard alloy, and is mechanically crushed into granular tungsten-containing waste material with a particle size of 1-3 mm; floor material, dust collecting material, grinding material and waste material produced in the production process of hard alloy; powdery tungsten-containing waste materials in floor materials, dust collecting materials and waste materials in the production process of tungsten carbide powder and tungsten powder; the tungsten-containing waste material comprises the following components:
tungsten 40-95% by mass;
2-20% of cobalt by mass; and
other impurities.
3. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the tungsten-containing waste in the step S1 is mixed with sulfuric acid in a mass ratio of 1: 0.2-1, mixing evenly; the mass percentage concentration of the sulfuric acid is more than 70%.
4. The method for preparing tungsten oxide from tungsten-containing waste material according to claim 1, wherein the roasting temperature in step S2 is 200 to 500 ℃.
5. The method for preparing tungsten oxide from tungsten-containing waste material according to claim 1, wherein the roasting time in step S2 is 1-5h.
6. The method for preparing tungsten oxide from tungsten-containing waste material according to claim 1, wherein the roasting atmosphere in step S2 is an oxidizing atmosphere, which may be one or more of air, oxygen-enriched air or oxygen.
7. The method for preparing tungsten oxide from tungsten-containing waste materials according to claim 1, wherein the acidified tail gas generated in the sulfating roasting process in the step S2 is washed by an acid washing circulating absorption system and then recycled.
8. The method for preparing tungsten oxide from tungsten-containing waste materials 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 the leaching time is 0.5-3h.
9. The method for preparing tungsten oxide from tungsten-containing waste material according to claim 1, wherein the stirring speed of the water immersion process of step S3 is 100-600r/min.
10. The method for preparing tungsten oxide from tungsten-containing waste according to claim 1, wherein the cobalt salt solution obtained in step S3 is purified by chemical precipitation to remove impurities, and then is used for preparing cobalt oxalate products by precipitating cobalt with ammonium oxalate or calcining cobalt oxalate to prepare cobalt oxide powder products.
11. The method for preparing tungsten oxide from tungsten-containing waste materials as claimed in claim 1, wherein the calcination temperature of the tungstic acid solid phase slag in the step S4 is 500-800 ℃.
12. The method for preparing tungsten oxide from tungsten-containing waste materials as claimed in claim 1, wherein the calcination time of the tungstic acid solid phase slag in the step S4 is 1-6h.
13. The method for preparing tungsten oxide from tungsten-containing waste materials as claimed in claim 1, wherein the tungstic acid solid phase residue in the step S3 can be directly calcined to prepare tungsten oxide products; or dissolving the tungstic acid solid-phase slag into an ammonium tungstate solution by using ammonia water, and preparing an ammonium paratungstate product after evaporation and crystallization; or dissolving the tungstic acid solid-phase slag into sodium tungstate solution by using alkaline leaching, obtaining ammonium tungstate solution by using an ion exchange process or an extraction process, and obtaining an ammonium paratungstate product by evaporating and crystallizing the ammonium tungstate solution.
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