CN108439473A - A kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide - Google Patents
A kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide Download PDFInfo
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- CN108439473A CN108439473A CN201810305267.XA CN201810305267A CN108439473A CN 108439473 A CN108439473 A CN 108439473A CN 201810305267 A CN201810305267 A CN 201810305267A CN 108439473 A CN108439473 A CN 108439473A
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- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 46
- 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 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 17
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000009514 concussion Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000005373 pervaporation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 7
- 230000008020 evaporation Effects 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WXFIGDLSSYIKKV-RCOVLWMOSA-N L-Metaraminol Chemical compound C[C@H](N)[C@H](O)C1=CC=CC(O)=C1 WXFIGDLSSYIKKV-RCOVLWMOSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide, belongs to tungsten waste recovery technology field；The method of the invention is：The tungsten waste of powdery is subjected to high temperature and pressure leaching with sodium hydroxide in stainless steel cauldron, sulfuric acid solution is added into the aqueous slkali of tungstenic and adjusts PH, makes PH controls 3 ~ 5, remains that solution is clarified；Into solution be added TOA and N235 combined extraction agent and sodium carbonate hydrogen ammonium extracted and be stripped, then it is heated evaporation, crystallization, drying, again calcining obtain nanometer tungsten oxide.The nanometer tungsten oxide that the method for the invention is prepared has the advantages that granularity is small and uniform；Soaking time in roasting process is shorter, ensure that the high advantage of the complete and crystallinity of particle.
Description
Technical field
The present invention relates to a kind of methods that tungstenic scrap hard alloy prepares nanometer tungsten oxide, belong to tungsten waste recycling skill
Art field.
Background technology
Tungsten is important strategy metal resource, is widely used in the fields such as space flight, military project, civilian and China is traditional
One of mineral of exporting goods and earning foreign currency；At history initial stage, China's tungsten resource is very abundant, but the extensive style exploitation passed through 60 years utilizes,
From accounting for the 65% of world saving when founding the state and dropping to 37.7%, advantage weakens rapidly the tungsten reserves in China；In addition, country also puts into effect
Relevant policies limit resource exploitation of mineral resources, and raw ore supply is becoming tight；The waste of tungsten ore resource is also very serious, to environment
Cause very big pollution.However, the dosage of tungsten but constantly increases with the development of society, insufficient to make up former tungsten resource content, give up tungsten
The research of recycling problem of industry is extremely urgent.
Hard alloy is usually carbide and binding metal refractory metals tungsten through having made of powder metallurgy process
The material of high rigidity, high-flexural strength, in necks such as machine-building, mining, communications and transportation, energy exploration, building decorations
Domain is widely used.However refractory metals tungsten and rare metal cobalt are particularly important strategy members generally acknowledged in the world
Element, on improving national economy, military competition power has very important influence.Currently, the tungsten resource that the whole world is more than 50% is used for
Hard alloy is manufactured, and the W content in scrap hard alloy just has reached 74%~91%, the annual consumption tungsten metal of China
About 2.7 ten thousand t, if the rate of recovery can reach 40%, for establishing Resources Guarantee System and promoting recycling economy development significant.
The oxide of tungsten has electro-chemical activity, can be used for lithium cell cathode material, oxygen reduction catalyst etc..Tungsten has four
Kind oxide, i.e. WO3、WO2.9、WO2.72And WO2；Various low price tungsten oxides can be oxidized to three under high temperature and oxidizing atmosphere
Tungsten oxide, the oxide that tungsten is obtained by control technique are the recycling of tungsten and prepare the effective way of valuable tungsten product.
It is at present the techniques such as to be leached, purified to it to obtain the tungsten of high-purity to the recovery process containing scrap hard alloy
Hydrochlorate, then tungstates is handled to obtain tungsten oxide, this complex process, influence factor is more in purification process so that tungsten
The rate of recovery it is low and of high cost.Also, meeting waste discharge, pollutes the environment in purification process.The present invention is directed to current
Technical problem, it is proposed that a kind of tungsten oxide granularity simple for process, at low cost, recycling is small and uniform process.
Invention content
The purpose of the present invention is to provide a kind of tungstenic scrap hard alloys come the method for producing nanometer tungsten oxide, specific packet
Include following steps：
（1）The processing of scrap hard alloy：By waste material calcining, broken, grind into powder, powder absolute ethyl alcohol and deionized water
It is dry after washing, then with sodium hydroxide solution（Waste material is all immersed in sodium hydroxide solution）Vacuum adds in autoclave
Thermal response generates sodium tungstate solution and precipitation, sodium tungstate solution is obtained by filtration；
（2）The processing of sodium tungstate solution：
1. in step（1）Sulfuric acid is added in obtained sodium tungstate solution and adjusts PH, makes solution PH control 3 ~ 5, is conducive to extract
The complexing of agent and tungstate radicle；
2. by trioctylamine（TOA）And N, N- dioctyl -1- octylames（N235）Combined extraction agent and isooctanol, sulfonated kerosene it is mixed
It closes, is then added in sodium tungstate solution and is extracted；
3. through shaking, detaching, tungstenic extract organic phase is obtained, enough ammonium bicarbonate solns are added in organic phase, passed through
Concussion, isolated ammonium tungstate solution；
4. ammonium tungstate solution obtains ammonium tungstate crystal through pervaporation, crystallization, by the drying of ammonium tungstate crystal, calcining obtains nanometer again
Tungsten oxide.
Preferably, step of the present invention（1）The condition of middle waste material calcining is：30min is raised to 200 DEG C of 30 ~ 70min of heat preservation,
120min is raised to 800 ~ 1000 DEG C, keeps the temperature 100 ~ 180min.
Preferably, step of the present invention（1）Middle concentration of sodium hydroxide solution is 8% ~ 12%.
Preferably, step of the present invention（1）The condition of middle heating in vacuum reaction is：3 ~ 5h of reaction time, reaction temperature 120 ~
160℃。
Preferably, step of the present invention（2）Described in trioctylamine and N, the volume of N- dioctyl -1- octylames in combined extraction agent
Than being 2:3~3:2, combined extraction agent, isooctanol, sulfonated kerosene volume ratio be 1:4:5~2:1:2.
Preferably, step of the present invention（2）Middle sodium tungstate solution, which shakes with extract liquor in ultrasonic constant-temperature slot, to be sufficiently mixed
It detaches again afterwards, the concussion time is 5 ~ 10min, shakes 30 ~ 45 DEG C of temperature.
Preferably, step of the present invention（2）Middle tungstenic extract organic phase is with ammonium bicarbonate soln in ultrasonic constant-temperature slot
Concussion detaches again after being sufficiently mixed, and the concussion time is 5 ~ 10min, shakes 30 ~ 45 DEG C of temperature.
Preferably, step of the present invention（2）70 ~ 80 DEG C, 4 ~ 6h of time of the evaporative crystallization temperature of middle ammonium tungstate solution, drying temperature
80 ~ 100 DEG C, 2 ~ 3h of time of degree, 550 ~ 700 DEG C of calcination temperature, 4 ~ 5h of time.
Beneficial effects of the present invention：
（1）The method of the invention present invention compared with being decomposed currently with acid and ammonia solvent recycles scrap hard alloy technique
Experimental period is short, it is easy to accomplish the continuity of experiment, but also can solve the problems, such as the spent acid occurred in sour decomposable process, simultaneously
Because equipment is simple, flow is short, overcomes the shortcomings that prior art precipitated crystal is separated by solid-liquid separation multistage operation in the process, improves
Production efficiency reduces reagent consumption.
（2）There is the present invention very high extraction yield, tungsten extraction yield to extract product up to 99% compared with conventional extraction method
Purity also can reach 95% or more, have very high economic benefit；In the complex being obtained by extraction, tungsten is uniform in complex
Distribution, the decomposition of the organic phase in roasting process around tungsten can effectively prevent the close to each other of tungsten particle, the group of avoiding
It is poly-, so that the nanometer tungsten oxide being prepared has many advantages, such as that granularity is small and uniform；Soaking time in roasting process compared with
It is short, it ensure that the high advantage of the complete and crystallinity of particle.Obtained nanometer tungsten oxide using its granularity it is small the advantages that as lithium
Ion battery cathode material also shows excellent chemical property.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Fig. 2 is the scanning electron microscopic picture for the nanometer tungsten oxide that the embodiment of the present invention 3 is prepared.
Fig. 3 is the XRD diffraction pictures for the nanometer tungsten oxide that the embodiment of the present invention 3 is prepared.
Specific implementation mode
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
The raw materials used trioctylamine of the embodiment of the present invention（Shanghai Aladdin biochemical technology limited liability company）, N, N- bis- is pungent
Base -1- octylames（Shanghai Aladdin biochemical technology limited liability company）It is commercial product.
Embodiment 1
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment（As shown in Figure 1）, specifically include following step
Suddenly：
（1）The processing of scrap hard alloy：Waste material is calcined（Calcination condition：30min is raised to 200 DEG C of heat preservations 50min, 120min
950 DEG C are raised to, 170min is kept the temperature）, broken, grind into powder, powder absolute ethyl alcohol and deionized water are dried after wash.
（2）Sodium hydroxide solution leaches：By powdered tungsten waste and sodium hydroxide solution in stainless steel cauldron
Heating in vacuum is reacted, and concentration of sodium hydroxide solution is 8%, reaction time 3h, 120 DEG C of reaction temperature, is generated sodium tungstate solution and is sunk
It forms sediment, sodium tungstate solution is obtained by filtration.
（3）The processing of sodium tungstate solution：
1. in step（2）Sulfuric acid is added in obtained sodium tungstate solution and adjusts PH, it is 3 to make solution PH；Sulfuric acid it is a concentration of
0.5mol/L。
2. the combined extraction agent of TOA and N235, isooctanol, sulfonated kerosene are pressed 1：2：7 ratios mix, wherein TOA with
N235 volume ratios are 2:3, sodium tungstate solution and extractant（The mixed liquor of above-mentioned four kinds of organic solvents）By 1:1 ratio mixes, will
Mixed liquor shakes in supersonic generator, shakes time 5min, shakes 30 DEG C of temperature, organic phase is then demultiplex out.
3. strippant ammonium bicarbonate soln is added into the organic phase obtained in 2., water is comparably 2:1；Mixed liquor is existed
It is shaken in supersonic generator, shakes time 5min, shaken 30 DEG C of temperature, ammonium tungstate solution is then demultiplex out.
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：70 DEG C, time 4h；It will
The drying of ammonium tungstate crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：80 DEG C, time 2h of drying temperature, calcination temperature
550 DEG C, time 4h.
The purity for the nanometer tungsten oxide that the present embodiment is prepared is 96.26%, and particle size distribution is uniform.
Embodiment 2
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment, specifically includes following steps：
（1）The processing of scrap hard alloy：Waste material is calcined（Calcination condition：30min is raised to 200 DEG C of heat preservations 60min, 120min
850 DEG C are raised to, 160min is kept the temperature）, broken, grind into powder, powder absolute ethyl alcohol and deionized water are dried after wash.
（2）Sodium hydroxide solution leaches：By powdered tungsten waste and sodium hydroxide solution in stainless steel cauldron
Heating in vacuum react, concentration of sodium hydroxide solution is 9%, reaction time 3.5h, 130 DEG C of reaction temperature, generate sodium tungstate solution and
Precipitation, is obtained by filtration sodium tungstate solution.
（3）The processing of sodium tungstate solution：
1. in step（2）In obtained sodium tungstate solution be added sulfuric acid adjust PH, make solution PH be 3.5, sulfuric acid it is a concentration of
0.7mol/L。
2. the combined extraction agent of TOA and N235, isooctanol, sulfonated kerosene are pressed 1：4：5 ratios mix, wherein TOA with
N235 volume ratios are 1:1, sodium tungstate solution and extractant（The mixed liquor of above-mentioned four kinds of organic solvents）By 1:1 ratio mixes, will
Mixed liquor shakes in supersonic generator, shakes time 5min, shakes 35 DEG C of temperature, organic phase is then demultiplex out.
3. strippant ammonium bicarbonate soln is added into the organic phase obtained in 2., water is comparably 2:1, by mixed liquor
It is shaken in supersonic generator, shakes time 5min, shaken 35 DEG C of temperature, ammonium tungstate solution is then demultiplex out.
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：80 DEG C, time 5h.It will
The drying of ammonium tungstate crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：80 DEG C, time 2.5h of drying temperature, calcining temperature
600 DEG C of degree, time 4h.
The purity for the nanometer tungsten oxide that the present embodiment is prepared is 95.86%, and particle size distribution is uniform.
Embodiment 3
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment, specifically includes following steps：
（1）The processing of scrap hard alloy：Waste material is calcined（Calcination condition：30min is raised to 200 DEG C of heat preservations 50min, 120min
900 DEG C are raised to, 150min is kept the temperature）, broken, grind into powder, powder absolute ethyl alcohol and deionized water are dried after wash.
（2）Sodium hydroxide solution leaches：By powdered tungsten waste and sodium hydroxide solution in stainless steel cauldron
Heating in vacuum is reacted, and concentration of sodium hydroxide solution is 10%, reaction time 3.5h, 140 DEG C of reaction temperature, generates sodium tungstate solution
And precipitation, sodium tungstate solution is obtained by filtration.
（3）The processing of sodium tungstate solution：
1. in step（2）In obtained sodium tungstate solution be added sulfuric acid adjust PH, make solution PH be 4, sulfuric acid it is a concentration of
0.5mol/L。
2. the combined extraction agent of TOA and N235, isooctanol, sulfonated kerosene are pressed 1：1：3 ratios mix, wherein TOA with
N235 volume ratios are 2:3, sodium tungstate solution and extractant（The mixed liquor of above-mentioned four kinds of organic solvents）By 1:1.5 ratios mix,
Mixed liquor is shaken in supersonic generator, shakes time 10min, 40 DEG C of temperature is shaken, organic phase is then demultiplex out.
3. strippant ammonium bicarbonate soln is added into the organic phase obtained in 2., water is comparably 2:1, by mixed liquor
It is shaken in supersonic generator, shakes time 10min, shaken 40 DEG C of temperature, ammonium tungstate solution is then demultiplex out.
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：75 DEG C, time 4h.It will
The drying of ammonium tungstate crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：90 DEG C, time 2h of drying temperature, calcination temperature
650 DEG C, time 4h.
The nanometer tungsten oxide scanning electron microscopic picture that the present embodiment is prepared into is as shown in Figure 2, it can be seen that roasting obtains
Tungsten oxide grain size belong to Nano grade, particle is tiny, be in nano bar-shape, and be distributed it is relatively uniform, pattern is preferable；It is nano oxidized
The XRD diffraction picture of tungsten understands that product major event is tungsten oxide as shown in figure 3, characteristic peak is compared with standard PDF cards, characteristic peak
Intensity is larger, illustrates that crystallinity is fine, and the displacement very little at peak shows brilliant pavilion dimensionally stable.
The purity for the nanometer tungsten oxide that the present embodiment is prepared is 97.23%, and particle size distribution is uniform.
Embodiment 4
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment, specifically includes following steps：
（1）The processing of scrap hard alloy：Waste material is calcined（Calcination condition：30min is raised to 200 DEG C of heat preservations 70min, 120min
1000 DEG C are raised to, 100min is kept the temperature）, broken, grind into powder, powder absolute ethyl alcohol and deionized water are dried after wash.
（2）Sodium hydroxide solution leaches：By powdered tungsten waste and sodium hydroxide solution in stainless steel cauldron
Heating reaction, concentration of sodium hydroxide solution is 10%, reaction time 3h, 150 DEG C of reaction temperature, generates sodium tungstate solution and precipitation,
Sodium tungstate solution is obtained by filtration.
（3）The processing of sodium tungstate solution：
1. in step（2）In obtained sodium tungstate solution be added sulfuric acid adjust PH, make solution PH be 5, sulfuric acid it is a concentration of
0.5mol/L。
2. the combined extraction agent of TOA and N235, isooctanol, sulfonated kerosene are pressed 2：1：2 ratios mix, wherein TOA with
N235 volume ratios are 3:2, sodium tungstate solution and extractant（The mixed liquor of above-mentioned four kinds of organic solvents）By 1:1.2 ratios mix,
Mixed liquor is shaken in supersonic generator, shakes time 5min, temperature 45 C is shaken, organic phase is then demultiplex out.
3. strippant ammonium bicarbonate soln is added into the organic phase obtained in 2., water is comparably 2:1, by mixed liquor
It is shaken in supersonic generator, shakes time 10min, shaken 35 DEG C of temperature, ammonium tungstate solution is then demultiplex out.
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：80 DEG C, time 5h.It will
The drying of ammonium tungstate crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：100 DEG C, time 3h of drying temperature, calcining temperature
680 DEG C of degree, time 4h.
The nanometer tungsten oxide purity that the present embodiment is prepared into is 95.82%, and particle size distribution is uniform.
Embodiment 5
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment, specifically includes following steps：
（1）The processing of scrap hard alloy：Waste material is calcined（Calcination condition：30min is raised to 200 DEG C of heat preservations 30min, 120min
800 DEG C are raised to, 180min is kept the temperature）, broken, grind into powder, powder absolute ethyl alcohol and deionized water are dried after wash.
（2）Sodium hydroxide solution leaches：By powdered tungsten waste and sodium hydroxide solution in stainless steel cauldron
Heating in vacuum react, concentration of sodium hydroxide solution is 12%, reaction time 4h, 145 DEG C of reaction temperature, generate sodium tungstate solution and
Precipitation, is obtained by filtration sodium tungstate solution.
（3）The processing of sodium tungstate solution：
1. in step（2）In obtained sodium tungstate solution be added sulfuric acid adjust PH, make solution PH be 4, sulfuric acid it is a concentration of
0.5mol/L。
2. the combined extraction agent of TOA and N235, isooctanol, sulfonated kerosene are pressed 2：1：7 ratios mix, wherein TOA with
N235 volume ratios are 1:1, sodium tungstate solution and extractant（The mixed liquor of above-mentioned four kinds of organic solvents）By 1:2 ratios mix, will
Mixed liquor shakes in supersonic generator, shakes time 8min, shakes temperature 45 C, organic phase is then demultiplex out.
3. strippant ammonium bicarbonate soln is added into the organic phase obtained in 2., water is comparably 1.5:1, it will mix
Liquid shakes in supersonic generator, shakes time 10min, shakes temperature 45 C, ammonium tungstate solution is then demultiplex out.
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：80 DEG C, time 4h.It will
The drying of ammonium tungstate crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：100 DEG C, time 2.5h of drying temperature, calcining
700 DEG C of temperature, time 4h.
The purity that the present embodiment prepares obtained nanometer tungsten oxide is 96.52%, and particle size distribution is uniform.
Comparative example
The method for preparing nanometer tungsten oxide with scrap hard alloy described in the present embodiment, specifically includes following steps：
（1）The pre-processing and sodium hydroxide solution leaching step and example of scrap hard alloy（3）In it is identical；
（2）The processing of sodium tungstate solution：
1. sulfuric acid is added in sodium tungstate solution adjusts PH, it is 4 to make solution PH, a concentration of 0.5mol/L of sulfuric acid.
2. aramine -336, sec-octyl alcohol, 260# solvent naphthas are pressed 1：1：3 ratios mix, wherein sodium tungstate solution and mixing
Extractant afterwards presses 1:1.5 ratios mix, and mixed liquor is shaken in supersonic generator, shake time 10min, shake temperature
40 DEG C, organic phase is then demultiplex out.
3. strippant ammonium hydroxide is added into the organic phase obtained in 2., water is comparably 2:1, by mixed liquor in ultrasonic wave
It is shaken in generator, shakes time 10min, shaken 40 DEG C of temperature, ammonium tungstate solution is then demultiplex out；
4. ammonium tungstate solution obtains ammonium tungstate crystal by heating evaporation, crystallization, heating condition is：75 DEG C, time 4h.By wolframic acid
The drying of ammonium crystal, calcining obtains nanometer tungsten oxide again, and roasting condition is：90 DEG C, time 2h of drying temperature, calcination temperature 650
DEG C, time 4h.
The nanometer tungsten oxide purity that this comparative example is prepared into is 91.43%, and grain diameter is larger.
Claims (8)
1. a kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide, which is characterized in that specifically include following steps：
（1）The processing of scrap hard alloy：By waste material calcining, broken, grind into powder, powder absolute ethyl alcohol and deionized water
It is dry after washing, then heating in vacuum is reacted in autoclave with sodium hydroxide solution, generates sodium tungstate solution and precipitation, mistake
Filter obtains sodium tungstate solution；
（2）The processing of sodium tungstate solution：
1. in step（1）Sulfuric acid is added in obtained sodium tungstate solution and adjusts PH, makes solution PH control 3 ~ 5；
2. by trioctylamine and N, the combined extraction agent of N- dioctyl -1- octylames is mixed with isooctanol, sulfonated kerosene, is then added to tungsten
It is extracted in acid sodium solution；
3. through shaking, detaching, tungstenic extract organic phase is obtained, enough ammonium bicarbonate solns are added in organic phase, passed through
Concussion, isolated ammonium tungstate solution；
4. ammonium tungstate solution obtains ammonium tungstate crystal through pervaporation, crystallization, by the drying of ammonium tungstate crystal, calcining obtains nanometer again
Tungsten oxide.
2. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（1）The condition of middle waste material calcining is：30min is raised to 200 DEG C of heat preservations 30 ~ 70min, 120min and is raised to 800 ~ 1000 DEG C, heat preservation
100~180min。
3. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（1）Middle concentration of sodium hydroxide solution is 8% ~ 12%.
4. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（1）The condition of middle heating in vacuum reaction is：3 ~ 5h of reaction time, 120 ~ 160 DEG C of reaction temperature.
5. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（2）Described in trioctylamine and N in combined extraction agent, the volume ratio of N- dioctyl -1- octylames is 2:3~3:2, it is combined extraction agent, different
Octanol, sulfonated kerosene volume ratio be 1:4:5~2:1:2.
6. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（2）Middle sodium tungstate solution shakes with extract liquor in ultrasonic constant-temperature slot be sufficiently mixed after detach again, the concussion time is 5 ~
10min shakes 30 ~ 45 DEG C of temperature.
7. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（2）Middle tungstenic extract organic phase is shaken with ammonium bicarbonate soln in ultrasonic constant-temperature slot be sufficiently mixed after detach again, shake
Time is 5 ~ 10min, shakes 30 ~ 45 DEG C of temperature.
8. the method that tungstenic scrap hard alloy according to claim 1 prepares nanometer tungsten oxide, it is characterised in that：Step
（2）70 ~ 80 DEG C, 4 ~ 6h of time of the evaporative crystallization temperature of middle ammonium tungstate solution, 80 ~ 100 DEG C, 2 ~ 3h of time of drying temperature, calcining
550 ~ 700 DEG C of temperature, 4 ~ 5h of time.
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| CN113697858A (en) * | 2021-07-23 | 2021-11-26 | 福建金鑫钨业股份有限公司 | Preparation method of tungstic acid |
| CN113697858B (en) * | 2021-07-23 | 2024-04-19 | 福建鑫鹭钨业有限公司 | Preparation method of tungstic acid |
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Application publication date: 20180824 |