CN113718268A - Method for recycling tungsten waste - Google Patents
Method for recycling tungsten waste Download PDFInfo
- Publication number
- CN113718268A CN113718268A CN202110823926.0A CN202110823926A CN113718268A CN 113718268 A CN113718268 A CN 113718268A CN 202110823926 A CN202110823926 A CN 202110823926A CN 113718268 A CN113718268 A CN 113718268A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- electrolysis
- molten salt
- waste
- tungsten waste
- 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 69
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 67
- 239000010937 tungsten Substances 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 229910001080 W alloy Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 3
- -1 tungsten ions Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000004506 ultrasonic cleaning Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 238000005498 polishing Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明提供一种回收钨废料的方法，所述方法包括：以包含碳酸盐的碱金属氯化物熔盐体系为电解质，以钨废料为工作电极，导电镀件为辅助电极，采用熔盐电解法对钨废料进行回收；其中将CO2作为碳源引入电解回收过程中。本发明创新地将CO2作为碳源引入钨二次资源回收中，钨废料被氧化时，钨以离子形式溶出，在电解初期碳酸盐中的碳酸根还原成碳与钨离子结合，与此同时，通入的CO2气体作为补充碳源，源源不断的输入到熔盐体系中，保证了体系中有充足的碳源与钨源结合生成WC。本发明实现了对钨二次资源的高效优质回收，且有利于降低空气中的CO2含量。
The invention provides a method for recycling tungsten waste, which comprises the following steps: using an alkali metal chloride molten salt system containing carbonate as an electrolyte, using tungsten waste as a working electrode, a conductive plating piece as an auxiliary electrode, and using molten salt electrolysis The tungsten waste is recovered by the method; in which CO2 is introduced into the electrolytic recovery process as a carbon source. The invention innovatively introduces CO2 as a carbon source into the recovery of tungsten secondary resources. When the tungsten waste is oxidized, tungsten is dissolved in the form of ions, and the carbonate in the carbonate in the early stage of electrolysis is reduced to carbon and combined with tungsten ions. At the same time, the incoming CO 2 gas is used as a supplementary carbon source, which is continuously input into the molten salt system, ensuring that there is sufficient carbon source in the system to combine with the tungsten source to generate WC. The invention realizes high-efficiency and high-quality recovery of tungsten secondary resources, and is beneficial to reduce the CO 2 content in the air.
Description
Technical Field
The invention relates to the field of molten salt electrochemistry, in particular to a method for recycling tungsten waste.
Background
Tungsten is a rare metal with high melting point, high specific gravity and high hardness, is widely applied to modern technologies in a pure metal state and an alloy state, and relates to various industrial fields of mines, metallurgy, machinery, construction, traffic, electronics, chemical engineering, light industry, textile, military industry, aerospace and the like, wherein the most important alloy state is alloy steel, tungsten carbide-based hard alloy, wear-resistant alloy and high-heat alloy.
Because of the wide application of tungsten resources, the recycling of tungsten secondary resources is very important. The existing recovery methods of tungsten secondary resources can be divided into two types, one type is that tungsten is subjected to chemical reaction by using a metallurgical method and is converted into tungsten salt, and tungsten powder products are recovered through steps of separation, purification, reduction and the like, the tungsten powder obtained by the method can be directly used or used after further processing, the method relates to a wet metallurgy process, and the method has the disadvantages of long flow, large amount of waste acid and waste liquid and large environmental load; the other type is that the tungsten does not generate chemical reaction, and gradient utilization products with the same type as the secondary resource products are obtained by methods such as physical crushing and the like, other impurities are inevitably introduced in the treatment process by the methods, and the product performance cannot be further improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for recovering tungsten waste by adding CO2The method introduces a tungsten secondary resource recovery process as a carbon source, realizes the preparation of tungsten carbide products by efficiently recovering tungsten wastes with high quality in a short process, and is favorable for reducing CO in the air2And (4) content.
The invention adopts the following technical scheme:
the invention provides a method for recycling tungsten waste, which comprises the following steps: taking an alkali metal chloride molten salt system containing carbonate as an electrolyte, taking tungsten waste as a working electrode and taking a conductive plating part as an auxiliary electrode, and recovering the tungsten waste by adopting a molten salt electrolysis method; wherein CO is introduced2As a carbon source to be introduced into the electrolytic recovery process.
At present, inert gas is introduced into the waste tungsten materials recovered by a molten salt electrolysis method in the electrolysis process, so that the electrodes are protected from being oxidized, tungsten powder products are obtained after electrolysis, and tungsten carbide can be obtained by further processing, namely the most common utilization mode of tungsten. The invention breaks the fixed thinking and innovatively puts forward CO2Introducing tungsten as carbon source into a tungsten secondary resource recovery process, taking tungsten waste as a working electrode in a carbonate-containing alkali metal chloride molten salt medium, wherein when the tungsten waste is oxidized, tungsten is dissolved out in an ion form, and in the initial stage of electrolysisCarbonate in carbonate is reduced into carbon which is combined with tungsten ions to generate tungsten carbide, and simultaneously, CO is introduced2Gas is used as a carbon source, and is continuously supplemented into a molten salt system, so that sufficient carbon source and a tungsten source are combined in the system to generate WC. The invention realizes the reasonable and recovery of tungsten secondary resources, does not need to process tungsten powder into tungsten carbide by a complex method, can realize the recovery and preparation of high-performance tungsten carbide nanopowder by a short process, and utilizes CO in the process2As a carbon source, it helps to achieve the goal of carbon neutralization.
Further, the present invention introduces CO2As the carbon source, certain conditions need to be met: heating the molten salt electrolyte to 400-2350-1000ppm argon gas mixture with a gas inlet flow of 80-150ml/min, and starting electrolysis.
Further, the carbonate is Na2CO3、K2CO3And Li2CO3The carbonate accounts for 0.5-4% of the mass fraction of the alkali metal chloride.
Further, the alkali metal chloride is one or more of NaCl, KCl and LiCl.
In a preferred embodiment of the invention, the alkali chloride consists of NaCl and KCl in a molar ratio of 1: 1; the carbonate is Na2CO3The alkali metal chloride accounts for 1-3% of the mass fraction of the alkali metal chloride.
Further, the surface roughness of the conductive plated part is less than Ra 1.6, and the conductivity is more than 240S/cm.
Further, the molten salt electrolysis method is constant current electrolysis or constant potential electrolysis.
Specifically, in the constant current electrolysis process, the current density is 40-200 mA/cm2The electrolysis time is 1-9 h.
In the constant potential electrolysis process, the potential is 1.5-4V, and the electrolysis time is 1-4 h.
In the invention, the tungsten waste comprises waste tungsten alloy, tungsten electrodes, waste hard alloy, tungsten-containing catalyst and the like. Wherein the waste tungsten alloy is WNiMoFe alloy, and tungsten carbide powder can be obtained by recycling the waste tungsten alloy; the hard alloy is composed of tungsten carbide and binder phase cobalt, and the tungsten carbide-cobalt powder can be obtained by recycling waste hard alloy.
In one embodiment of the present invention, the method for recycling tungsten scrap comprises the following steps:
s1, polishing the tungsten rod to remove rust, cleaning and drying for later use;
s2, processing the conductive plating piece until the surface roughness is less than Ra 1.6, cleaning and drying for later use;
s3, mixing the raw materials of the molten salt electrolyte which is subjected to vacuum drying and dehydration in advance according to a ratio, opening a vacuum valve, heating to 200-300 ℃ under a vacuum condition, preserving heat for 2-4h, uniformly dissolving, and closing the vacuum valve after heat preservation is finished;
s4, heating the molten salt electrolyte to 400-2350-1000ppm argon gas mixture with the gas inlet flow of 80-150 ml/min;
s5, placing the auxiliary electrode and the working electrode in a molten salt electrolyte containing CO2In the atmosphere, a constant current (current density of 40-200 mA/cm) is carried out2) Or electrolyzing at a constant potential (the potential is 1.5-4V), cooling, taking out the working electrode and the auxiliary electrode, washing with water, centrifuging, drying and collecting the product in the reactor.
Wherein, the drying in the step S5 is forced air drying, the temperature is 50-60 ℃, and the drying time is 10-12 h.
The tungsten carbide powder prepared by the method has the purity of over 99 percent and can be used as a high-end product.
The invention provides a method for recycling tungsten waste, which innovatively uses CO2Introducing the carbon source into the recovery of tungsten secondary resource, taking tungsten waste as a working electrode and a conductive plating part as an auxiliary electrode in a carbonate-containing alkali metal chloride molten salt medium, dissolving out tungsten in the form of ions when the tungsten waste is oxidized, reducing carbonate in the initial stage of electrolysis into carbon and combining the carbon with the tungsten ions, and introducing CO simultaneously2Gas is used as a supplementary carbon source and is continuously input into a molten salt system,ensuring that sufficient carbon source and tungsten source are combined to generate WC in the system. The invention realizes the high-efficiency and high-quality recovery of the tungsten secondary resource and is beneficial to reducing the CO in the air2And (4) content.
Drawings
FIG. 1 is an XRD pattern of WC powder obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of WC powder obtained in example 2 of the present invention;
FIG. 3 is an XRD pattern of WC powder obtained in example 3 of the present invention;
FIG. 4 is an XRD pattern of the powder obtained in comparative example 1 of the present invention;
FIG. 5 is an XRD pattern of the powder obtained in comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a method for recycling waste tungsten alloy, which comprises the following specific steps:
s1, sequentially placing the tungsten alloy rod subjected to mechanical cutting and polishing treatment in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s2, mechanically grinding and polishing the surface of the conductive plated part until the surface is smooth, sequentially placing the conductive plated part in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s3, drying NaCl and KCl in a vacuum drying oven at 200 ℃ for 24 hours in advance, and dehydrating;
s4, weighing the dehydrated NaCl and KCl according to the molar ratio of 1:1, and adding Na accounting for 2% of the mass fraction of the chloride2CO3Putting the mixed salt into a resistance furnace, opening a vacuum valve, heating to 300 ℃ under a vacuum condition, preserving heat for 2 hours to obtain molten salt which is uniformly melted, and closing the vacuum valve after the heat preservation is finished;
s5, heating the molten salt electrolyte to 750 ℃, preserving heat for 2h, and introducing CO2350ppm of argon gas mixture, the gas inflow is 80 ml/min;
s6, placing the auxiliary electrode and the working electrode in a molten salt electrolyte, connecting an electrochemical workstation, and placing the electrochemical workstation in the electrolyte containing CO2In the atmosphere, a constant potential electrolysis technology is adopted, the voltage is set to be 2.4V, and electrolysis is carried out for 3 hours; during electrolysis, CO is detected in outlet gas2Reduced to 100ppm and containing product O2。
S7, after the electrolysis is finished, taking out the working electrode, sequentially carrying out ultrasonic cleaning in alcohol and deionized water, and then washing with clean water to remove the salt attached to the surface of the coating; and (3) washing the product obtained in the crucible with water, centrifuging, and drying by air blowing for 10 hours at the temperature of 60 ℃.
Fig. 1 is an XRD pattern of the WC powder obtained in this example, and it can be seen that the product contains no impurity phase other than the WC phase.
Example 2
The embodiment provides a method for recycling waste tungsten alloy, which comprises the following specific steps:
s1, sequentially placing the tungsten alloy rod subjected to mechanical cutting and polishing treatment in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s2, mechanically grinding and polishing the surface of the conductive plated part until the surface is smooth, sequentially placing the conductive plated part in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s3, drying NaCl and KCl in a vacuum drying oven at 200 ℃ for 24 hours in advance, and dehydrating;
s4, weighing the dehydrated NaCl and the dehydrated K according to the molar ratio of 1:1Cl, and then Na accounting for 2 percent of the mass fraction of the chlorine salt is added2CO3Putting the mixed salt into a resistance furnace, opening a vacuum valve, heating to 300 ℃ under a vacuum condition, preserving heat for 2 hours to obtain molten salt which is uniformly melted, and closing the vacuum valve after the heat preservation is finished;
s5, heating the molten salt electrolyte to 750 ℃, preserving heat for 2h, and introducing CO2550ppm argon gas mixture, with the gas inflow of 100 ml/min;
s6, placing the auxiliary electrode and the working electrode in a molten salt electrolyte, connecting an electrochemical workstation, and placing the electrochemical workstation in the electrolyte containing CO2In the atmosphere, constant current electrolysis technology is adopted, and the set voltage is 200mA/cm2Carrying out electrolysis for 5 hours; during electrolysis, CO is detected in outlet gas2The content was reduced to 300 ppm.
S7, after the electrolysis is finished, taking out the working electrode, sequentially carrying out ultrasonic cleaning in alcohol and deionized water, and then washing with clean water to remove the salt attached to the surface of the coating; and (3) washing the product obtained in the crucible with water, centrifuging, and drying by air blowing for 10 hours at the temperature of 60 ℃.
Fig. 2 is an XRD pattern of the WC powder prepared in this example, and it can be seen that the product contains no impurity phase other than the WC phase.
Example 3
The embodiment provides a method for recycling waste tungsten alloy, which comprises the following specific steps:
s1, sequentially placing the tungsten alloy rod subjected to mechanical cutting and polishing treatment in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s2, mechanically grinding and polishing the surface of the conductive plated part until the surface is smooth, sequentially placing the conductive plated part in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s3, drying LiCl and KCl in a vacuum drying oven at 200 ℃ for 24 hours in advance, and dehydrating;
s4, weighing the LiCl and the KCl after dehydration according to the molar ratio of 3:2, and then adding Li accounting for 2 percent of the mass fraction of the chloride2CO3Putting the mixed salt into a resistance furnace, opening a vacuum valve, and vacuumizingHeating to 300 ℃ under the condition, preserving heat for 2 hours to obtain molten salt which is uniformly melted, and closing a vacuum valve after heat preservation is finished;
s5, heating the molten salt electrolyte to 450 ℃, keeping the temperature for 2h, and introducing CO21000ppm of argon gas mixture, with the gas inflow rate of 150 ml/min;
s6, placing the auxiliary electrode and the working electrode in a molten salt electrolyte, connecting an electrochemical workstation, and placing the electrochemical workstation in the electrolyte containing CO2In the atmosphere, a constant current electrolysis technology is adopted, and the current is set to be 100mA/cm2Carrying out electrolysis for 7 hours; during electrolysis, CO is detected in outlet gas2The content was reduced to 600 ppm.
S7, after the electrolysis is finished, taking out the working electrode, sequentially carrying out ultrasonic cleaning in alcohol and deionized water, and then washing with clean water to remove the salt attached to the surface of the coating; and (3) washing the product obtained in the crucible with water, centrifuging, and drying by air blowing for 10 hours at the temperature of 60 ℃.
Fig. 3 is an XRD pattern of the WC powder prepared in this example, and it can be seen that the product contains no impurity phase other than the WC phase.
Comparative example 1
The comparative example provides a method for recycling waste tungsten alloy, which comprises the following specific steps:
s1, sequentially placing the waste tungsten alloy subjected to mechanical cutting and polishing treatment into alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s2, mechanically grinding and polishing the surface of the conductive plated part until the surface is smooth, sequentially placing the conductive plated part in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s3, drying LiCl and KCl in a vacuum drying oven at 200 ℃ for 24 hours in advance, and dehydrating;
s4, weighing the LiCl and the KCl after dehydration according to the molar ratio of 1:1, and then adding Li accounting for 2 percent of the mass fraction of the chloride2CO3Putting the mixed salt into a resistance furnace, opening a vacuum valve, heating to 300 ℃ under a vacuum condition, preserving heat for 2 hours to obtain molten salt which is uniformly melted, and closing the vacuum valve after the heat preservation is finished;
s5, opening an air inlet valve, introducing high-purity argon, introducing 150ml/min of air inlet flow, and keeping the temperature for 2 hours after the temperature is raised to 450 ℃;
s6, placing the auxiliary electrode and the working electrode in a molten salt electrolyte, connecting an electrochemical workstation, and electrolyzing for 7 hours in an Ar atmosphere by adopting a constant potential electrolysis technology and setting the voltage to be 2.4V;
s7, after the electrolysis is finished, taking out the working electrode, sequentially carrying out ultrasonic cleaning in alcohol and deionized water, and then washing with clean water to remove the salt attached to the surface of the coating; and (3) washing the product obtained in the crucible with water, centrifuging, and drying by air blowing for 10 hours at the temperature of 60 ℃.
FIG. 4 is an XRD pattern of the powder obtained in this comparative example, and it can be seen that the content of lithium tungstate hydrate as an impurity phase is high in addition to the WC product phase because CO is not introduced during the electrolysis2Atmosphere, resulting in no supplemental source of carbonate in the molten salt.
Comparative example 2
The comparative example provides a method for recycling waste tungsten alloy, which comprises the following specific steps:
s1, sequentially placing the waste tungsten alloy subjected to mechanical cutting and polishing treatment into alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s2, mechanically grinding and polishing the surface of the conductive plated part until the surface is smooth, sequentially placing the conductive plated part in alcohol and deionized water for ultrasonic cleaning, and drying for later use;
s3, drying LiCl and KCl in a vacuum drying oven at 200 ℃ for 24 hours in advance, and dehydrating;
s4, weighing the dehydrated LiCl and KCl according to the molar ratio of 1:1, putting the mixed salt into a resistance furnace, opening a vacuum valve, heating to 300 ℃ under the vacuum condition, preserving the heat for 2 hours to obtain uniformly melted molten salt, and closing the vacuum valve after the heat preservation is finished;
s5, opening an air inlet valve and introducing CO2800ppm argon gas mixture with the gas inflow rate of 100ml/min, and keeping the temperature for 2 hours after the temperature is raised to 450 ℃;
s6, auxiliary electrode and workingThe electrodes are placed in a molten salt electrolyte, connected to an electrochemical workstation, and contain CO2In the atmosphere, a constant potential electrolysis technology is adopted, the voltage is set to be 2.4V, and electrolysis is carried out for 7 hours;
s7, after the electrolysis is finished, taking out the working electrode, sequentially carrying out ultrasonic cleaning in alcohol and deionized water, and then washing with clean water to remove the salt attached to the surface of the coating; and (3) washing the product obtained in the crucible with water, centrifuging, and drying by air blowing for 10 hours at the temperature of 60 ℃.
FIG. 5 is an XRD pattern of the powder obtained in this comparative example, and it can be seen that the product is mainly tungsten powder and contains a certain amount of WC due to the absence of carbonate concentration in the initial molten salt system and the direct introduction of CO2Can not be dissolved in the molten salt well, and can not provide carbon source at the cathode.
In summary, the method for recycling tungsten waste provided by the invention is implemented by mixing CO2The method is used as a carbon source to introduce a tungsten secondary resource recovery process under appropriate conditions, realizes the high-efficiency and high-quality recovery of tungsten waste materials in a short process, and is favorable for reducing CO in the air2And (4) content.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823926.0A CN113718268A (en) | 2021-07-21 | 2021-07-21 | Method for recycling tungsten waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823926.0A CN113718268A (en) | 2021-07-21 | 2021-07-21 | Method for recycling tungsten waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113718268A true CN113718268A (en) | 2021-11-30 |
Family
ID=78673620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110823926.0A Pending CN113718268A (en) | 2021-07-21 | 2021-07-21 | Method for recycling tungsten waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113718268A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875422A (en) * | 2022-03-31 | 2022-08-09 | 湖北绿钨资源循环有限公司 | Method for efficiently and environmentally preparing tungsten carbide powder through molten salt electrolysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018190A (en) * | 2014-06-17 | 2014-09-03 | 北京工业大学 | Method for recovering waste hard alloy |
| CN108044126A (en) * | 2017-11-27 | 2018-05-18 | 崇义章源钨业股份有限公司 | The method that platy structure WC-Co composite powder end is prepared using scrap hard alloy |
| CN108149279A (en) * | 2017-11-30 | 2018-06-12 | 北京工业大学 | The method that electrolysis discarded hard alloy directly prepares tungsten-base alloy powder |
| CN110923776A (en) * | 2019-12-18 | 2020-03-27 | 武汉大学 | Mixing CO2Conversion to metal carbide coating and O2Molten salt electrochemical process of |
-
2021
- 2021-07-21 CN CN202110823926.0A patent/CN113718268A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018190A (en) * | 2014-06-17 | 2014-09-03 | 北京工业大学 | Method for recovering waste hard alloy |
| CN108044126A (en) * | 2017-11-27 | 2018-05-18 | 崇义章源钨业股份有限公司 | The method that platy structure WC-Co composite powder end is prepared using scrap hard alloy |
| CN108149279A (en) * | 2017-11-30 | 2018-06-12 | 北京工业大学 | The method that electrolysis discarded hard alloy directly prepares tungsten-base alloy powder |
| CN110923776A (en) * | 2019-12-18 | 2020-03-27 | 武汉大学 | Mixing CO2Conversion to metal carbide coating and O2Molten salt electrochemical process of |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875422A (en) * | 2022-03-31 | 2022-08-09 | 湖北绿钨资源循环有限公司 | Method for efficiently and environmentally preparing tungsten carbide powder through molten salt electrolysis |
| CN114875422B (en) * | 2022-03-31 | 2024-05-31 | 湖北绿钨资源循环有限公司 | Method for efficiently and environmentally preparing tungsten carbide powder by fused salt electrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10519556B2 (en) | Process for recycling waste carbide | |
| CN100415940C (en) | Method for producing pure titanium by anodic electrolysis of titanium monoxide/titanium carbide soluble solid solution | |
| Li et al. | A review on the extraction and recovery of critical metals using molten salt electrolysis | |
| CN104561550B (en) | A kind of method that aluminothermic reduction ilmenite prepares Al Ti Fe alloys in ice crystal ground mass fused salt | |
| CN106544701B (en) | With the method for the metal in electrolysis of fluorides recovered WC waste material | |
| CN105177635B (en) | A kind of continuous system and method for preparing tungsten powder | |
| CN110684902B (en) | Process for extracting noble metal by silver capture of high-alumina oil catalyst | |
| CN108642522A (en) | A kind of recovery method of the waste material containing indium | |
| CN103305694A (en) | Method for recovering tungsten carbide and metal cobalt from waste hard alloy | |
| CN110129572B (en) | Method for preparing high-purity ammonium rhenate by using waste nickel-based high-temperature alloy | |
| CN113718268A (en) | Method for recycling tungsten waste | |
| JP7122315B2 (en) | Electrode, method for producing same, and method for producing regenerated electrode | |
| PL111879B1 (en) | Method of recovery of copper from diluted acid solutions | |
| CN105714332A (en) | Method for electrodepositing vanadium through fused salt | |
| EP1995353A1 (en) | METHOD OF REMOVING/CONCENTRATING METAL-FOG-FORMING METAL PRESENT IN MOLTEN SALT, APPARATUS THEREFOR, AND PROCESS AND APPARATUS FOR PRODUCING Ti OR Ti ALLOY BY USE OF THEM | |
| CN106893859A (en) | A kind of method for processing nickel cobalt waste material | |
| CN106893860A (en) | It is a kind of to process the method containing antimony sulphide ore | |
| JP2019085618A (en) | Recovery method of antimony | |
| US3589987A (en) | Method for the electrolytic preparation of tungsten carbide | |
| CN114059103A (en) | Method for recovering tungsten carbide and cobalt from waste hard alloy | |
| CN113512740B (en) | Method for preparing WC-Co composite powder by using waste hard alloy | |
| CN113832344B (en) | Method for recovering copper and cobalt from copper-cobalt slag | |
| CN105063660B (en) | A kind of method that nano-silicon powder is directly prepared in electrorefining processes | |
| CN114645300B (en) | Preparation method for directly dechlorinating cuprous chloride and circularly regenerating copper | |
| Murphy et al. | Recovery of Lead from Galena by a Leach Electrolysis Procedure |
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 |