CN109796046A - A kind of preparation process of high-purity ammonium paratungstate - Google Patents
A kind of preparation process of high-purity ammonium paratungstate Download PDFInfo
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- CN109796046A CN109796046A CN201910214082.2A CN201910214082A CN109796046A CN 109796046 A CN109796046 A CN 109796046A CN 201910214082 A CN201910214082 A CN 201910214082A CN 109796046 A CN109796046 A CN 109796046A
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Abstract
The invention discloses a kind of preparation processes of high-purity ammonium paratungstate, the following steps are included: one, raw material tungsten block is milled to 2400 mesh, it is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, it is filtered with plate and frame filter press, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, obtain sodium tungstate solution, ammonium chloride is added in sodium tungstate solution, obtain ammonium paratungstate-sodium double salt, five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into ammonium paratungstate；The present invention dissolves raw material in the way of electrolytic catalysis, and filtering while removes nonmetallic inclusion, then obtains the higher ammonium paratungstate product of purity by ammonium paratungstate-sodium double salt legal system, reaches the standard of APT-0, be worth promoting.
Description
Technical field
The present invention relates to ammonium paratungstate processing technique field, the preparation process of specifically a kind of high-purity ammonium paratungstate.
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..
Ammonium paratungstate (APT) is a kind of important tungsten intermediate products, mainly white crystals, there is sheet or two kinds needle-shaped,
For manufacturing tungstic acid or blue tungsten oxide metal tungsten powder, the quality of tungsten product is heavily dependent on the chemistry of APT
Purity, granular size and size distribution etc..
Ammonium paratungstate is a kind of important inorganic salt product, and China uses for a long time is added sodium carbonate, sodium nitrate with wolframite
Be sintered, be crushed, leach coarse sodium tungstate, through molten decompose of removal of impurities, artificial scheelite, acid be made that wolframic acid, ammonium be molten, evaporative crystallization
Obtain ammonium paratungstate product.
Such as disclose application No. is the Chinese patent of CN201610677960.0 " including removal of impurities: water logging is gone out into filtrate and is existed
Under condition of heating and stirring, sulfuric acid is added, ammonium chloride and Adlerika is then added, then acid adding is boiled, and filters to remove after standing
Miscellaneous filtrate；Removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；Except molybdenum: will remove
Heavy metal filtrate is heated to boiling under condition of heating and stirring after sulfuric acid is added, and refilters except molybdenum filtrate；Acid extract: it will remove
Molybdenum filtrate, is extracted in extraction tank, obtains the strip liquor containing tungstic acid；Evaporative crystallization: strip liquor is put into reaction kettle
It is interior, it is evaporated crystallization under stirring, heating condition, obtains ammonium paratungstate after washing, drying.Raw material wide adaptation range, clean journey
Sequence is simple, and process flow is short, and tungsten high income, stable product quality, physical and chemical performance is good, and equipment investment is small, energy-saving, raw
It produces at low cost "
The ammonium paratungstate preparation process flow of such as above-mentioned patent is complex, tediously long.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation processes of high-purity ammonium paratungstate that technique is relatively simple, to solve
The problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 8-10min for the revolving speed of 800-900r/min, and moderate-speed mixer is the revolving speed of 1200-1400r/min
Stir 15-18min, high-speed stirred be 2000-2400r/min revolving speed stir 10-15min, using tungstic acid as anode electrode,
Lead to electrocatalytic reaction by cathode electrode of the carbon-point of graphene modified, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
As a further solution of the present invention: the pre-heat treatment being carried out to NaOH in the step 3, is heated to 50-60
℃。
As a further solution of the present invention: in the filtrate II when concentration < 30g/L of NaCl, being supplemented into filtrate II
It is recycled after ammonium chloride to predetermined concentration；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, into
Enter in step 6 and handles together.
As a further solution of the present invention: in the step 4 molar ratio of sodium tungstate and ammonium chloride be 1:(1.5~
4)。
As a further solution of the present invention: sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: chlorination is added
After ammonium solid, it is stirred to react 0.5~3h at a temperature of being placed in 50~95 DEG C, then stands 2~8h of heat preservation at such a temperature.
As a further solution of the present invention: the preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 8min for the revolving speed of 800r/min, and the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high
The revolving speed that speed stirring is 2000r/min stirs 10min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
As a further solution of the present invention: the preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 8min for the revolving speed of 850r/min, and the revolving speed that moderate-speed mixer is 1250r/min stirs 15min, high
The revolving speed that speed stirring is 2150r/min stirs 10min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
As a further solution of the present invention: the preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 9min for the revolving speed of 880r/min, and the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high
The revolving speed that speed stirring is 2200r/min stirs 11min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
As a further solution of the present invention: the preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 9min for the revolving speed of 880r/min, and the revolving speed that moderate-speed mixer is 1300r/min stirs 17min, high
The revolving speed that speed stirring is 2300r/min stirs 13min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled
As a further solution of the present invention:
As further scheme of the invention:.
Compared with prior art, the beneficial effects of the present invention are: the present invention carries out raw material in the way of electrolytic catalysis
Dissolution, filtering while, remove nonmetallic inclusion, then obtain the higher ammonium paratungstate of purity by ammonium paratungstate-sodium double salt legal system
Product reaches the standard of APT-0；
The still further aspect present invention reduces the dosage of ammonium chloride, reduces life by the way that ammonium chloride is prepared for sodium chloride
Produce cost.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment one
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 8min for the revolving speed of 800r/min, and the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high
The revolving speed that speed stirring is 2000r/min stirs 10min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
The pre-heat treatment is carried out to NaOH in the step 3, is heated to 50-60 DEG C.
In the filtrate II when concentration < 30g/L of NaCl, recycled after supplementing ammonium chloride to predetermined concentration into filtrate II
It uses；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in six and handles together.
The molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4 in the step 4).
Sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: after chloride solid is added, be placed in 50~95 DEG C
At a temperature of be stirred to react 0.5~3h, then at such a temperature stand heat preservation 2~8h.
The Testing index of the present embodiment output ammonium paratungstate product is as follows:
Embodiment two
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 8min for the revolving speed of 850r/min, and the revolving speed that moderate-speed mixer is 1250r/min stirs 15min, high
The revolving speed that speed stirring is 2150r/min stirs 10min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
The pre-heat treatment is carried out to NaOH in the step 3, is heated to 50-60 DEG C.
In the filtrate II when concentration < 30g/L of NaCl, recycled after supplementing ammonium chloride to predetermined concentration into filtrate II
It uses；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in six and handles together.
The molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4 in the step 4).
Sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: after chloride solid is added, be placed in 50~95 DEG C
At a temperature of be stirred to react 0.5~3h, then at such a temperature stand heat preservation 2~8h.
The Testing index of the present embodiment output ammonium paratungstate product is as follows:
Embodiment three
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 9min for the revolving speed of 880r/min, and the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high
The revolving speed that speed stirring is 2200r/min stirs 11min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
The pre-heat treatment is carried out to NaOH in the step 3, is heated to 50-60 DEG C.
In the filtrate II when concentration < 30g/L of NaCl, recycled after supplementing ammonium chloride to predetermined concentration into filtrate II
It uses；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in six and handles together.
The molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4 in the step 4).
Sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: after chloride solid is added, be placed in 50~95 DEG C
At a temperature of be stirred to react 0.5~3h, then at such a temperature stand heat preservation 2~8h.
The Testing index of the present embodiment output ammonium paratungstate product is as follows:
Example IV
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 9min for the revolving speed of 880r/min, and the revolving speed that moderate-speed mixer is 1300r/min stirs 17min, high
The revolving speed that speed stirring is 2300r/min stirs 13min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
The pre-heat treatment is carried out to NaOH in the step 3, is heated to 50-60 DEG C.
In the filtrate II when concentration < 30g/L of NaCl, recycled after supplementing ammonium chloride to predetermined concentration into filtrate II
It uses；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in six and handles together.
The molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4 in the step 4).
Sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: after chloride solid is added, be placed in 50~95 DEG C
At a temperature of be stirred to react 0.5~3h, then at such a temperature stand heat preservation 2~8h.
The Testing index of the present embodiment output ammonium paratungstate product is as follows:
Embodiment five
A kind of preparation process of high-purity ammonium paratungstate, comprising the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the journey of gradient stirring
Sequence includes stirring at low speed to stir 10min for the revolving speed of 900r/min, and the revolving speed that moderate-speed mixer is 1400r/min stirs 18min, high
The revolving speed that speed stirring is 2400r/min stirs 15min, is negative using tungstic acid as anode electrode, with the carbon-point of graphene modified
Pole electrode leads to electrocatalytic reaction, stands 80min；
Two, be filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, the nonmetallic inclusions such as arsenic, removal of impurities filtrate into
Enter next program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate
Solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains para-tungstic acid
Ammonium-sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, is converted into ammonium paratungstate-sodium double salt
Ammonium paratungstate, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean,
Obtain ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride
With filtrate II I；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains chlorine
Change ammonium and filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, ammonium chloride returns
Step 4 and step 5 are recycled.
The pre-heat treatment is carried out to NaOH in the step 3, is heated to 50-60 DEG C.
In the filtrate II when concentration < 30g/L of NaCl, recycled after supplementing ammonium chloride to predetermined concentration into filtrate II
It uses；In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in six and handles together.
The molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4 in the step 4).
Sodium tungstate and ammonium chloride reaction process in the step 4 are as follows: after chloride solid is added, be placed in 50~95 DEG C
At a temperature of be stirred to react 0.5~3h, then at such a temperature stand heat preservation 2~8h.
The Testing index of the present embodiment output ammonium paratungstate product is as follows:
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 (9)
1. a kind of preparation process of high-purity ammonium paratungstate, which comprises the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the program bag of gradient stirring
It includes to stir at low speed and stirs 8-10min for the revolving speed of 800-900r/min, the revolving speed that moderate-speed mixer is 1200-1400r/min stirs
15-18min, the revolving speed that high-speed stirred is 2000-2400r/min stirs 10-15min, using tungstic acid as anode electrode, with stone
The carbon-point of black alkene modification is that cathode electrode leads to electrocatalytic reaction, stands 80min；
Two, it is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, under removal of impurities filtrate enters
One program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains ammonium paratungstate-
Sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into secondary tungsten
Sour ammonium, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean, obtain
Ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride and filter
Liquid III；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains ammonium chloride
With filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride, ammonium chloride return step using Hou's process for soda production
Four and step 5 be recycled.
2. the preparation process of high-purity ammonium paratungstate according to claim 1, which is characterized in that right in the step 3
NaOH carries out the pre-heat treatment, is heated to 50-60 DEG C.
3. the preparation process of high-purity ammonium paratungstate according to claim 1, which is characterized in that NaCl in the filtrate II
Concentration < 30g/L when, into filtrate II supplement ammonium chloride to predetermined concentration after be recycled；The concentration of NaCl in filtrate II >=
When 30g/L, filtrate II is merged with filtrate I, enters step in six and handles together.
4. the preparation process of high-purity ammonium paratungstate according to claim 1, which is characterized in that wolframic acid in the step 4
The molar ratio of sodium and ammonium chloride is 1:(1.5~4).
5. the preparation process of high-purity ammonium paratungstate according to claim 1, which is characterized in that wolframic acid in the step 4
Sodium and ammonium chloride reaction process are as follows: after chloride solid is added, 0.5~3h is stirred to react at a temperature of being placed in 50~95 DEG C, so
Stand 2~8h of heat preservation at such a temperature afterwards.
6. the preparation process of high-purity ammonium paratungstate according to claim 1, which comprises the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the program bag of gradient stirring
It includes to stir at low speed and stirs 8min for the revolving speed of 800r/min, the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high-speed stirring
It mixes and stirs 10min for the revolving speed of 2000r/min, using tungstic acid as anode electrode, electric by cathode of the carbon-point of graphene modified
Extremely logical electrocatalytic reaction, stands 80min；
Two, it is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, under removal of impurities filtrate enters
One program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains ammonium paratungstate-
Sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into secondary tungsten
Sour ammonium, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean, obtain
Ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride and filter
Liquid III；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains ammonium chloride
With filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride, ammonium chloride return step using Hou's process for soda production
Four and step 5 be recycled.
7. the preparation process of high-purity ammonium paratungstate according to claim 1, which comprises the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the program bag of gradient stirring
It includes to stir at low speed and stirs 8min for the revolving speed of 850r/min, the revolving speed that moderate-speed mixer is 1250r/min stirs 15min, high-speed stirring
It mixes and stirs 10min for the revolving speed of 2150r/min, using tungstic acid as anode electrode, electric by cathode of the carbon-point of graphene modified
Extremely logical electrocatalytic reaction, stands 80min；
Two, it is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, under removal of impurities filtrate enters
One program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains ammonium paratungstate-
Sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into secondary tungsten
Sour ammonium, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean, obtain
Ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride and filter
Liquid III；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains ammonium chloride
With filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride, ammonium chloride return step using Hou's process for soda production
Four and step 5 be recycled.
8. the preparation process of high-purity ammonium paratungstate according to claim 1, which comprises the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the program bag of gradient stirring
It includes to stir at low speed and stirs 9min for the revolving speed of 880r/min, the revolving speed that moderate-speed mixer is 1200r/min stirs 15min, high-speed stirring
It mixes and stirs 11min for the revolving speed of 2200r/min, using tungstic acid as anode electrode, electric by cathode of the carbon-point of graphene modified
Extremely logical electrocatalytic reaction, stands 80min；
Two, it is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, under removal of impurities filtrate enters
One program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains ammonium paratungstate-
Sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into secondary tungsten
Sour ammonium, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean, obtain
Ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride and filter
Liquid III；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains ammonium chloride
With filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride, ammonium chloride return step using Hou's process for soda production
Four and step 5 be recycled.
9. the preparation process of high-purity ammonium paratungstate according to claim 1, which comprises the following steps:
One, raw material tungsten block is milled to 2400 mesh, is placed in agitator and the stirring of concentrated sulfuric acid gradient is added, the program bag of gradient stirring
It includes to stir at low speed and stirs 9min for the revolving speed of 880r/min, the revolving speed that moderate-speed mixer is 1300r/min stirs 17min, high-speed stirring
It mixes and stirs 13min for the revolving speed of 2300r/min, using tungstic acid as anode electrode, electric by cathode of the carbon-point of graphene modified
Extremely logical electrocatalytic reaction, stands 80min；
Two, it is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, under removal of impurities filtrate enters
One program；
Three, continue that NaOH is added dropwise into removal of impurities filtrate under PH meter detection, until PH=7, acquired solution is sodium tungstate solution；
Four, ammonium chloride is added in sodium tungstate solution, reacts sodium tungstate and ammonium chloride sufficiently, separation of solid and liquid obtains ammonium paratungstate-
Sodium double salt and filtrate I；
Five, ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, and ammonium paratungstate-sodium double salt is made to be converted into secondary tungsten
Sour ammonium, separation of solid and liquid obtain thick ammonium paratungstate and filtrate II, using dilute ammonium chloride solution by thick ammonium paratungstate washes clean, obtain
Ammonium paratungstate；
Six, sodium chloride is precipitated: so that the sodium chloride in filtrate I is crystallized precipitation by being concentrated by evaporation, heat filtering obtains sodium chloride and filter
Liquid III；
Seven, ammonium chloride is precipitated: filtrate II I is handled by way of directly cooling or be concentrated by evaporation, separation of solid and liquid obtains ammonium chloride
With filtrate IV, enters in step 6 after filtrate IV is merged with filtrate I and handle together；
Eight, sodium chloride obtained by step 6 is prepared by sodium carbonate and ammonium chloride, ammonium chloride return step using Hou's process for soda production
Four and step 5 be recycled.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960469A (en) * | 2020-07-30 | 2020-11-20 | 湖南信力新材料有限公司 | Method for producing ammonium paratungstate by using tungsten-containing waste |
| CN113816427A (en) * | 2021-10-21 | 2021-12-21 | 江西钨业股份有限公司 | Crystallization process of ammonium paratungstate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643245A (en) * | 2008-08-05 | 2010-02-10 | 江西稀有稀土金属钨业集团有限公司 | Process for preparing high-purity ammonium paratungstate |
| CN103103359A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for regenerating APT (ammonium paratungstate) by use of APT waste low-grade tungsten slag |
| CN103952550A (en) * | 2014-04-25 | 2014-07-30 | 云南锡业集团有限责任公司研究设计院 | Comprehensive method for producing ammonium paratungstate through low-tungsten tin concentrate |
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN106673064A (en) * | 2016-12-05 | 2017-05-17 | 荆门德威格林美钨资源循环利用有限公司 | Method for producing ammonium paratungstate |
| CN107572588A (en) * | 2017-09-08 | 2018-01-12 | 丁明 | A kind of environment-friendly type sodium tungstate preparation technology and its application |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
| CN109019691A (en) * | 2018-10-10 | 2018-12-18 | 江西省修水赣北钨业有限公司 | A kind of preparation process of ammonium paratungstate |
| CN109052477A (en) * | 2018-10-18 | 2018-12-21 | 谭琴 | A kind of sodium tungstate preparation process being used to prepare ammonium paratungstate |
-
2019
- 2019-03-20 CN CN201910214082.2A patent/CN109796046A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643245A (en) * | 2008-08-05 | 2010-02-10 | 江西稀有稀土金属钨业集团有限公司 | Process for preparing high-purity ammonium paratungstate |
| CN103103359A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for regenerating APT (ammonium paratungstate) by use of APT waste low-grade tungsten slag |
| CN103952550A (en) * | 2014-04-25 | 2014-07-30 | 云南锡业集团有限责任公司研究设计院 | Comprehensive method for producing ammonium paratungstate through low-tungsten tin concentrate |
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN106673064A (en) * | 2016-12-05 | 2017-05-17 | 荆门德威格林美钨资源循环利用有限公司 | Method for producing ammonium paratungstate |
| CN107572588A (en) * | 2017-09-08 | 2018-01-12 | 丁明 | A kind of environment-friendly type sodium tungstate preparation technology and its application |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
| CN109019691A (en) * | 2018-10-10 | 2018-12-18 | 江西省修水赣北钨业有限公司 | A kind of preparation process of ammonium paratungstate |
| CN109052477A (en) * | 2018-10-18 | 2018-12-21 | 谭琴 | A kind of sodium tungstate preparation process being used to prepare ammonium paratungstate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960469A (en) * | 2020-07-30 | 2020-11-20 | 湖南信力新材料有限公司 | Method for producing ammonium paratungstate by using tungsten-containing waste |
| CN113816427A (en) * | 2021-10-21 | 2021-12-21 | 江西钨业股份有限公司 | Crystallization process of ammonium paratungstate |
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