CN109761283A - A kind of technique for the restoring tungsten oxide handling waste tungsten oxide - Google Patents
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide Download PDFInfo
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- CN109761283A CN109761283A CN201910214085.6A CN201910214085A CN109761283A CN 109761283 A CN109761283 A CN 109761283A CN 201910214085 A CN201910214085 A CN 201910214085A CN 109761283 A CN109761283 A CN 109761283A
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Abstract
The invention discloses a kind of techniques of restoring tungsten oxide for handling waste tungsten oxide, the following steps are included: the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, the ammonium tungstate solution that will be cooled to room temperature passes through vacuum filtration or centrifugal filtration or filters pressing, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is put into togerther vacuumfilter together with ammonium para-tungstate crystal or filter centrifugal filters, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3~4r/min, delivery rate is 190~320kg/h, temperature is 780~950 DEG C, ammonium paratungstate is reduced to blue tungsten oxide；The present invention, which directly passes through after ammonium hydroxide dissolves waste tungsten oxide, obtains ammonium paratungstate product, restores to obtain blue oxide tungsten product, simple process effectively recycles waste tungsten oxide, is worth promoting.
Description
Technical field
The present invention relates to tungsten oxide processing technique field, the work of the restoring tungsten oxide of specifically a kind of processing waste tungsten oxide
Skill.
Background technique
Tungsten is a kind of metallic element.The chemical elemental symbol of tungsten is W, and atomic number is 74, and relative atomic mass is
183.85, atomic radius is 137 micromicrons, and density is 19.35 grams/cubic centimeter, belongs in the periodic table of elements period 6 (the
Two long periods) group vib.Tungsten is mainly in sexavalence cation in nature, and ionic radius is 0.68 × 10-10m.Due to W6+
Ionic radius is small, and electricity price is high, and polarizability is strong, easily formation complex anion, therefore main [WO4] 2- in the form of complex anion of tungsten,
Is combined to form wolframite or scheelite precipitating with cations such as Fe2+, Mn2+, Ca2+ in solution.Tungsten after smelting is silver
The glossiness metal of white, fusing point is high, and hardness is very big, and vapour pressure is very low, and evaporation rate is also smaller, and chemical property is also relatively more steady
It is fixed.
Tungsten is a kind of rare metal.Rare metal is often referred to that content in nature is less or the dilute scattered metal of distribution.Tungsten
It is a kind of general element distributed more widely, almost all over seeing in each rocks, but content is lower.Content of the tungsten in the earth's crust be
0.001%, 1.5 × 10-6 of content average out in granite, this characteristic cause its extraction difficulty very big, are typically only capable to use
Organic solvent extractionprocess and Strong acid ion-exchanger extract.As the progress of science and technology and metallurgical technology, equipment and analysis are examined
The development of survey technology and the production-scale expansion of rare metal, so that the purity of tungsten is continuously improved, performance is continuously improved, kind
It is increasing, to expand the application field of tungsten.
Tungsten is a kind of strategy metal.It is well known that rare metal is the grand strategy resource of country, and tungsten is typical dilute
There is metal, there is particularly important purposes.It is the important component of contemporary high technology new material, a series of electron-optical materials
Material, specific alloy, new function material and organo-metallic compound etc. are both needed to the tungsten using special performance.Though dosage is less,
But most important, lacking it can not.Thus it is widely used in contemporary mechanics of communication, electronic computer, aerospace exploitation, medical and health, sense
Luminescent material, photoelectric material, energy and material and catalyst material etc..
Tungsten waste material is a kind of secondary tungsten resource, its recycling has high economic value.Into the eighties, state
Outer main tungsten country of consumption specially establishes recycling again if the U.S., Japan and Germany take much count of the recycling of tungsten waste material
Life structure.The tungsten that these countries recycle from useless tungsten material every year, the 25%-30% of Zhan Dangnian CEMENTED CARBIDE PRODUCTION tungsten amount.
China also compares attention to the reclaiming of tungsten waste material.The fifties latter stage, which has begun, carries out plant-scale hard alloy scraps
It is recycled work.Such as just there is nitre fusion method to recycle this content of alloy from waste in the Technology design of Zhuzhou Hard Alloy Plant.
The factory starts recycling, processing hard alloy scraps after in 1958 goes into operation, but quantity is little, and the rate of recovery is also relatively low, and
Environment is polluted, the further development of recovery operation is hindered.Since early seventies, new processing method is sought by China, takes
Obtained effect.Present Chinese Cemented Carbide Industry, annual about 500 tons of hard alloy scraps of recovery processing.Recovery method has nitre molten
Melt method, zinc melts method, oxidizing process, electrolysis method and acid extracting etc..Both Secondary resource has been developed and used, valuable gold has been recycled for country
Belong to tungsten and cobalt, and increases the economic benefit of enterprise.It is estimated according to domestic relevant expert, in the recuperable hard alloy scraps of China
Quantity reaches 40% of yield or more.Therefore, it should further take measures, reinforce this very significant work.
It is greatly waste tungsten oxide product in tungsten waste material, this kind of product is usually that wolframic acid is made in dissolution in recycling
Ammonium, ammonium paratungstate or ammonium metatungstate product, can further be made oxidation tungsten product.
Summary of the invention
Waste tungsten oxide dissolution is then reduced into as the place of blue oxide tungsten product the purpose of the present invention is to provide a kind of
The technique for managing the restoring tungsten oxide of waste tungsten oxide, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, is constantly stirring
Mixing lower slow heating, to be warming up to 4~10kg/cm2 of steam pressure in kettle most appropriate, and the autoclaving reaction time is that 60~180min is anti-
It should terminate, stop heating, be cooled to 20~40 DEG C, check solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear,
Adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed be 3~4r/min, delivery rate be 190~
320kg/h, temperature are 780~950 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
As a further solution of the present invention: temperature directly cooling is 0~10 DEG C in the step 4.
As a further solution of the present invention: furnace gas pressure is 0.2~0.8kPa in the step 5.
As a further solution of the present invention: it includes following mistake that ammonium paratungstate, which is reduced to blue tungsten oxide, in the step 5
Journey: ammonium paratungstate heat resolve is at tungstic acid, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
As a further solution of the present invention: handling the technique of the restoring tungsten oxide of waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, is constantly stirring
Mixing lower slow heating, to be warming up to 4~10kg/cm2 of steam pressure in kettle most appropriate, and the autoclaving reaction time is that 60~180min is anti-
It should terminate, stop heating, be cooled to 20~40 DEG C, check solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear,
Adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed be 3r/min, delivery rate 190kg/h,
Temperature is 780 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
As a further solution of the present invention: handling the technique of the restoring tungsten oxide of waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, is constantly stirring
Mixing lower slow heating, to be warming up to 4~10kg/cm2 of steam pressure in kettle most appropriate, and the autoclaving reaction time is that 60~180min is anti-
It should terminate, stop heating, be cooled to 20~40 DEG C, check solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear,
Adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 200kg/
H, temperature are 810 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
As a further solution of the present invention: handling the technique of the restoring tungsten oxide of waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, is constantly stirring
Mixing lower slow heating, to be warming up to 4~10kg/cm2 of steam pressure in kettle most appropriate, and the autoclaving reaction time is that 60~180min is anti-
It should terminate, stop heating, be cooled to 20~40 DEG C, check solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear,
Adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 220kg/
H, temperature are 850 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
As a further solution of the present invention: handling the technique of the restoring tungsten oxide of waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, is constantly stirring
Mixing lower slow heating, to be warming up to 4~10kg/cm2 of steam pressure in kettle most appropriate, and the autoclaving reaction time is that 60~180min is anti-
It should terminate, stop heating, be cooled to 20~40 DEG C, check solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear,
Adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.8r/min, delivery rate 260kg/
H, temperature are 890 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
Compared with prior art, the beneficial effects of the present invention are: the present invention directly passes through ammonium hydroxide to waste tungsten oxide progress
Obtain ammonium paratungstate product after dissolution, restore to obtain blue oxide tungsten product, simple process, effectively to waste tungsten oxide into
Row recycling.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment one
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed be 3r/min, delivery rate 190kg/h,
Temperature is 780 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Embodiment two
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 200kg/
H, temperature are 810 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Embodiment three
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 220kg/
H, temperature are 850 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Example IV
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.8r/min, delivery rate 260kg/
H, temperature are 890 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Embodiment five
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed be 4r/min, delivery rate 320kg/h,
Temperature is 950 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Embodiment six
A kind of technique for the restoring tungsten oxide handling waste tungsten oxide, comprising the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to oxidation
The weight of tungsten, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining.
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, compresses kettle cover,
Slow heating is warming up in kettle steam pressure in 0.5kg/cm under constant stirring2More than, for safe operation and the time is saved,
Steam pressure is in kettle with 4~10kg/cm2It is most appropriate, according to the granularity thickness of pressure in kettle and tungsten oxide, autoclaving reaction time
For 20~320min, for safe operation and the time is saved, the autoclaving reaction time is most appropriate with 60~180min, reaction knot
Beam stops heating, is cooled to room temperature (20~40 DEG C), checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear
It loses, adjusting the concentration of free ammonia with ammonium hydroxide or water is 3~5%, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/
l。
Three, the ammonium tungstate solution that will be cooled to room temperature is transferred to wolframic acid by vacuum filtration or centrifugal filtration or filters pressing, filtrate
Ammonium salt solution storage tank stands 10~30h, and the purpose of standing is that remaining part foreign ion in solution is made to be precipitated and tie by ageing
Crystalline substance is deposited to slot bottom.
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, solution is connected
It is put into togerther vacuumfilter or filter centrifugal filtering with ammonium para-tungstate crystal, is washed with water 3~4 times；
The directly cooling temperature is 0~10 DEG C.
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.9r/min, delivery rate 310kg/
H, temperature are 920 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide；
The furnace gas pressure is 0.2~0.8kPa.
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in step 5: ammonium paratungstate heat resolve is at three oxidations
Tungsten, ammonia and vapor；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen
Gas；
Tungstic acid is reduced into blue tungsten oxide.
Fsss, oxygen index (OI) and the residual ammonia percentage of the blue tungsten oxide in embodiment one to six, statistical result are detected respectively
It is as follows:
| Fsss/um | Oxygen index (OI) | Residual ammonia % | |
| Embodiment one | 13.35 | 2.93 | 0.13 |
| Embodiment two | 13.33 | 2.92 | 0.13 |
| Embodiment three | 13.21 | 2.81 | 0.12 |
| Example IV | 12.95 | 2.81 | 0.12 |
| Embodiment five | 12.89 | 2.78 | 0.10 |
| Embodiment six | 12.85 | 2.77 | 0.10 |
As can be seen from the above table, the granularity of blue tungsten oxide obtained by various embodiments of the present invention is excellent, has lower oxygen
Index and less residual ammonia, it is best in quality.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (8)
1. a kind of technique for the restoring tungsten oxide for handling waste tungsten oxide, which comprises the following steps:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to tungsten oxide
Weight, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, under constant stirring
Slow heating is warming up to 4~10kg/cm of steam pressure in kettle2Most appropriate, the autoclaving reaction time is 60~180min reaction knot
Beam stops heating, is cooled to 20~40 DEG C, checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear, uses ammonia
It is 3~5% that water or water, which adjust the concentration of free ammonia, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, it will be cooled to the ammonium tungstate solution of room temperature by vacuum filtration or centrifugal filtration or filters pressing, it is molten that filtrate is transferred to ammonium tungstate
Liquid storage tank 10~30h of standing, the purpose of standing are to make remaining part foreign ion in solution that crystallization be precipitated and sink by ageing
It forms sediment to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, by solution together with secondary
Wolframic acid crystalline ammonium is put into togerther vacuumfilter or filter centrifugal filtering, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed be 3~4r/min, delivery rate be 190~
320kg/h, temperature are 780~950 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
2. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that the step
Temperature directly cooling is 0~10 DEG C in four.
3. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that the step
Furnace gas pressure is 0.2~0.8kPa in five.
4. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that the step
It includes following procedure that ammonium paratungstate, which is reduced to blue tungsten oxide, in five: ammonium paratungstate heat resolve is at tungstic acid, ammonia and water
Steam；
Tungsten oxide is the good catalyst property that ammonia decomposes, and decomposites the ammonia come and is further broken into nitrogen and hydrogen；
Tungstic acid is reduced into blue tungsten oxide.
5. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that including following
Step:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to tungsten oxide
Weight, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, under constant stirring
It is most appropriate that slow heating is warming up to 4~10kg/cm2 of steam pressure in kettle, and the autoclaving reaction time is 60~180min reaction knot
Beam stops heating, is cooled to 20~40 DEG C, checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear, uses ammonia
It is 3~5% that water or water, which adjust the concentration of free ammonia, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, it will be cooled to the ammonium tungstate solution of room temperature by vacuum filtration or centrifugal filtration or filters pressing, it is molten that filtrate is transferred to ammonium tungstate
Liquid storage tank 10~30h of standing, the purpose of standing are to make remaining part foreign ion in solution that crystallization be precipitated and sink by ageing
It forms sediment to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, by solution together with secondary
Wolframic acid crystalline ammonium is put into togerther vacuumfilter or filter centrifugal filtering, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3r/min, delivery rate 190kg/h, temperature
It is 780 DEG C, ammonium paratungstate is reduced to blue tungsten oxide.
6. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that including following
Step:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to tungsten oxide
Weight, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, under constant stirring
It is most appropriate that slow heating is warming up to 4~10kg/cm2 of steam pressure in kettle, and the autoclaving reaction time is 60~180min reaction knot
Beam stops heating, is cooled to 20~40 DEG C, checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear, uses ammonia
It is 3~5% that water or water, which adjust the concentration of free ammonia, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, it will be cooled to the ammonium tungstate solution of room temperature by vacuum filtration or centrifugal filtration or filters pressing, it is molten that filtrate is transferred to ammonium tungstate
Liquid storage tank 10~30h of standing, the purpose of standing are to make remaining part foreign ion in solution that crystallization be precipitated and sink by ageing
It forms sediment to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, by solution together with secondary
Wolframic acid crystalline ammonium is put into togerther vacuumfilter or filter centrifugal filtering, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 200kg/h, temperature
Degree is 810 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
7. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that including following
Step:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to tungsten oxide
Weight, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, under constant stirring
It is most appropriate that slow heating is warming up to 4~10kg/cm2 of steam pressure in kettle, and the autoclaving reaction time is 60~180min reaction knot
Beam stops heating, is cooled to 20~40 DEG C, checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear, uses ammonia
It is 3~5% that water or water, which adjust the concentration of free ammonia, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, it will be cooled to the ammonium tungstate solution of room temperature by vacuum filtration or centrifugal filtration or filters pressing, it is molten that filtrate is transferred to ammonium tungstate
Liquid storage tank 10~30h of standing, the purpose of standing are to make remaining part foreign ion in solution that crystallization be precipitated and sink by ageing
It forms sediment to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, by solution together with secondary
Wolframic acid crystalline ammonium is put into togerther vacuumfilter or filter centrifugal filtering, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.5r/min, delivery rate 220kg/h, temperature
Degree is 850 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
8. the technique of the restoring tungsten oxide of processing waste tungsten oxide according to claim 1, which is characterized in that including following
Step:
One, the weight for determining tungsten oxide to be processed is precalculated according to the dischargeable capacity of autoclave, further according to tungsten oxide
Weight, which calculates, determines required weak aqua ammonia volume, or according to the weight of weak aqua ammonia volume calculating tungsten oxide needed for determining；
Two, the desired amount of weak aqua ammonia and waste tungsten oxide material is added into autoclave under stiring, under constant stirring
It is most appropriate that slow heating is warming up to 4~10kg/cm2 of steam pressure in kettle, and the autoclaving reaction time is 60~180min reaction knot
Beam stops heating, is cooled to 20~40 DEG C, checks solution colour, such as aobvious blue, then add hydrogen peroxide to blue and disappear, uses ammonia
It is 3~5% that water or water, which adjust the concentration of free ammonia, and controlling tungstic acid concentration in ammonium tungstate solution is 120~350g/l；
Three, it will be cooled to the ammonium tungstate solution of room temperature by vacuum filtration or centrifugal filtration or filters pressing, it is molten that filtrate is transferred to ammonium tungstate
Liquid storage tank 10~30h of standing, the purpose of standing are to make remaining part foreign ion in solution that crystallization be precipitated and sink by ageing
It forms sediment to slot bottom；
Four, ammonium tungstate solution is handled by way of directly cooling or evaporative crystallization, ammonium paratungstate is precipitated, by solution together with secondary
Wolframic acid crystalline ammonium is put into togerther vacuumfilter or filter centrifugal filtering, is washed with water 3~4 times；
Five, ammonium paratungstate is put into rotary electric furnace and is heated, electric furnace revolving speed is 3.8r/min, delivery rate 260kg/h, temperature
Degree is 890 DEG C, and ammonium paratungstate is reduced to blue tungsten oxide.
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