CN109943735A - A kind of technique preparing ammonium paratungstate with tungsten waste - Google Patents
A kind of technique preparing ammonium paratungstate with tungsten waste Download PDFInfo
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- CN109943735A CN109943735A CN201910224426.8A CN201910224426A CN109943735A CN 109943735 A CN109943735 A CN 109943735A CN 201910224426 A CN201910224426 A CN 201910224426A CN 109943735 A CN109943735 A CN 109943735A
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Abstract
The invention discloses a kind of techniques for preparing ammonium paratungstate with tungsten waste, comprising the following steps: one, pretreatment of raw material；Two, water logging goes out；Three, it cleans；Four, removing heavy metals；Five, molybdenum is removed；Six, acid extract, evaporative crystallization；Seven, double salt；Eight, it converts；Nine, sodium chloride is precipitated；Ten, ammonium chloride is precipitated；11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, the sodium carbonate may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled；The present invention prepares ammonium paratungstate from tungsten waste using leaching, extraction and ammonium sodium double salt method, the effective tungsten recycled in tungsten waste, and tungsten oxide can be further prepared by ammonium paratungstate, and the quality grade of gained ammonium paratungstate product is higher；The present invention is by the way that by the salt bearing liquid wastes generated in the process, effectively recycling, recycling reduce process costs, be worth promoting.
Description
Technical field
The present invention relates to ammonium paratungstate preparation technical field, specifically a kind of work that ammonium paratungstate is prepared with tungsten waste
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.
Ammonium paratungstate is a kind of chemical substance, mainly white crystals, there is sheet or two kinds needle-shaped, for manufacturing three oxidations
Tungsten or blue tungsten oxide metal tungsten powder.The present invention considers to prepare ammonium paratungstate with tungsten waste, so that it is useless to play recycling tungstenic
The effect of tungsten in material.
Summary of the invention
Para-tungstic acid is prepared from tungsten waste using leaching, extraction and ammonium sodium double salt method the purpose of the present invention is to provide a kind of
The technique of ammonium, 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 preparing ammonium paratungstate with tungsten waste, comprising the following steps:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, in reverberatory furnace
Interior 600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling first being worn into pulpous state, is then placed in metal trough, is heated after being diluted with water
To boiling, refilters to be made and leach filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 8.5-11 with sulfuric acid；By every
m3Saturated ammonium chloride and Adlerika 20-50 liter is added in material liquid, stirs 1.5-3 hours；Again with sulfuric acid tune PH to 8.5-
10.5；It boils 2-4 hours, stands 2-6 hours；It is filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, arsenic etc. are non-
Metal impurities, removal of impurities filtrate enter next program；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: by removing heavy metals filtrate, under condition of heating and stirring, being heated to boiling after sulfuric acid is added, refilter to remove
Molybdenum filtrate；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted, is obtained containing the anti-of tungstic acid in extraction tank
Extract liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, makes sodium tungstate and chlorination
Ammonium sufficiently reacts, and separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, turns ammonium paratungstate-sodium double salt
Ammonium paratungstate is turned to, and separation of solid and liquid is obtained thick ammonium paratungstate and filtrate II, thick ammonium paratungstate washed using dilute ammonium chloride solution
Completely, ammonium paratungstate is obtained；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride, the carbonic acid using Hou's process for soda production
Sodium may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled.
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 9 and handles together.
As a further solution of the present invention: in the step 7, the molar ratio of sodium tungstate and ammonium chloride be 1:(1.5~
4)。
As a further solution of the present invention: in the step 7, sodium tungstate and ammonium chloride reaction process 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: in the step 8, the mass concentration of ammonium chloride solution is 25%~30%.
As a further solution of the present invention: in the step 8, ammonium chloride solution and ammonium paratungstate-sodium double salt liquid are solid
Than for (4~6): 1.
As a further solution of the present invention: in the step 8, ammonium paratungstate-sodium double salt is converted into the temperature of ammonium paratungstate
Degree is 85~95 DEG C, and transformation time is 20~40min.
As a further solution of the present invention: in the step 10, directly cooling temperature is 0~10 DEG C, is separated by solid-liquid separation
Obtained ammonium chloride return step three, step 7 and step 8 is recycled.
As a further solution of the present invention: in the step 10, filtrate II I is handled by the way of evaporation and concentration, is controlled
Liquor capacity is 0.25~0.4 times of original volume after system concentration, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and
Step 8 is recycled.
Compared with prior art, the beneficial effects of the present invention are: the present invention using leach, extraction and ammonium sodium double salt method are from containing
Tungsten waste material prepares ammonium paratungstate, the effective tungsten recycled in tungsten waste, and oxidation can be further prepared by ammonium paratungstate
The quality grade of tungsten, gained ammonium paratungstate product is higher；
The present invention is by the way that by the salt bearing liquid wastes generated in the process, effectively recycling, recycling reduce technique
Cost.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment one
A kind of technique preparing ammonium paratungstate with tungsten waste, comprising the following steps:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, in reverberatory furnace
Interior 600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling first being worn into pulpous state, is then placed in metal trough, is heated after being diluted with water
To boiling, refilters to be made and leach filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 8.5 with sulfuric acid；By every m3
Saturated ammonium chloride and 20 liters of Adlerika are added in material liquid, stir 1.5 hours；Again with sulfuric acid tune PH to 8.5；It boils 2 hours,
Stand 2 hours；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；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: by removing heavy metals filtrate, under condition of heating and stirring, being heated to boiling after sulfuric acid is added, refilter to remove
Molybdenum filtrate；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted, is obtained containing the anti-of tungstic acid in extraction tank
Extract liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, makes sodium tungstate and chlorination
Ammonium sufficiently reacts, and separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, turns ammonium paratungstate-sodium double salt
Ammonium paratungstate is turned to, and separation of solid and liquid is obtained thick ammonium paratungstate and filtrate II, thick ammonium paratungstate washed using dilute ammonium chloride solution
Completely, ammonium paratungstate is obtained；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride, the carbonic acid using Hou's process for soda production
Sodium may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled.
In filtrate II when the concentration < 30g/L of NaCl, it is recycled after supplementing ammonium chloride to predetermined concentration into filtrate II；
In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in nine and handles together.
In the step 7, the molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4).
In the step 7, sodium tungstate and ammonium chloride reaction process 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.
In the step 8, the mass concentration of ammonium chloride solution is 25%~30%, the ammonium chloride solution and para-tungstic acid
Ammonium-sodium double salt liquid-solid ratio is (4~6): 1.
In the step 8, the temperature that ammonium paratungstate-sodium double salt is converted into ammonium paratungstate is 85~95 DEG C, and transformation time is
20~40min.
In the step 10, directly cooling temperature is 0~10 DEG C, the ammonium chloride return step three being separated by solid-liquid separation,
Step 7 and step 8 are recycled.
In the step 10, filtrate II I is handled by the way of evaporation and concentration, liquor capacity is original volume after control concentration
0.25~0.4 times, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and step 8 are recycled.
Its chemical component is as follows: sodium paratungstate product after above-mentioned process after testing
It can be seen that sodium paratungstate product obtained by the present invention fully meets the standard of GradeAPT-0 from above-mentioned table.
Embodiment two
The following steps are included:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, in reverberatory furnace
Interior 600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling first being worn into pulpous state, is then placed in metal trough, is heated after being diluted with water
To boiling, refilters to be made and leach filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 9 with sulfuric acid；By every m3Object
Saturated ammonium chloride and 25 liters of Adlerika are added in feed liquid, stir 2 hours；Again with sulfuric acid tune PH to 9；It boils 2-4 hours, stands
3 hours；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；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: by removing heavy metals filtrate, under condition of heating and stirring, being heated to boiling after sulfuric acid is added, refilter to remove
Molybdenum filtrate；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted, is obtained containing the anti-of tungstic acid in extraction tank
Extract liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, makes sodium tungstate and chlorination
Ammonium sufficiently reacts, and separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, turns ammonium paratungstate-sodium double salt
Ammonium paratungstate is turned to, and separation of solid and liquid is obtained thick ammonium paratungstate and filtrate II, thick ammonium paratungstate washed using dilute ammonium chloride solution
Completely, ammonium paratungstate is obtained；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride, the carbonic acid using Hou's process for soda production
Sodium may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled.
In filtrate II when the concentration < 30g/L of NaCl, it is recycled after supplementing ammonium chloride to predetermined concentration into filtrate II；
In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in nine and handles together.
In the step 7, the molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4).
In the step 7, sodium tungstate and ammonium chloride reaction process 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.
In the step 8, the mass concentration of ammonium chloride solution is 25%~30%, the ammonium chloride solution and para-tungstic acid
Ammonium-sodium double salt liquid-solid ratio is (4~6): 1.
In the step 8, the temperature that ammonium paratungstate-sodium double salt is converted into ammonium paratungstate is 85~95 DEG C, and transformation time is
20~40min.
In the step 10, directly cooling temperature is 0~10 DEG C, the ammonium chloride return step three being separated by solid-liquid separation,
Step 7 and step 8 are recycled.
In the step 10, filtrate II I is handled by the way of evaporation and concentration, liquor capacity is original volume after control concentration
0.25~0.4 times, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and step 8 are recycled.
Its chemical component is as follows: sodium paratungstate product after above-mentioned process after testing
It can be seen that sodium paratungstate product obtained by the present invention fully meets the standard of GradeAPT-0 from above-mentioned table.
Embodiment three
The following steps are included:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, in reverberatory furnace
Interior 600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling first being worn into pulpous state, is then placed in metal trough, is heated after being diluted with water
To boiling, refilters to be made and leach filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 10 with sulfuric acid；By every m3Object
Saturated ammonium chloride and 40 liters of Adlerika are added in feed liquid, stir 2 hours；Again with sulfuric acid tune PH to 9；It boils 3 hours, stands 4
Hour；It is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, removal of impurities filtrate enters next
Program；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: by removing heavy metals filtrate, under condition of heating and stirring, being heated to boiling after sulfuric acid is added, refilter to remove
Molybdenum filtrate；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted, is obtained containing the anti-of tungstic acid in extraction tank
Extract liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, makes sodium tungstate and chlorination
Ammonium sufficiently reacts, and separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, turns ammonium paratungstate-sodium double salt
Ammonium paratungstate is turned to, and separation of solid and liquid is obtained thick ammonium paratungstate and filtrate II, thick ammonium paratungstate washed using dilute ammonium chloride solution
Completely, ammonium paratungstate is obtained；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride, the carbonic acid using Hou's process for soda production
Sodium may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled.
In filtrate II when the concentration < 30g/L of NaCl, it is recycled after supplementing ammonium chloride to predetermined concentration into filtrate II；
In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in nine and handles together.
In the step 7, the molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4).
In the step 7, sodium tungstate and ammonium chloride reaction process 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.
In the step 8, the mass concentration of ammonium chloride solution is 25%~30%, the ammonium chloride solution and para-tungstic acid
Ammonium-sodium double salt liquid-solid ratio is (4~6): 1.
In the step 8, the temperature that ammonium paratungstate-sodium double salt is converted into ammonium paratungstate is 85~95 DEG C, and transformation time is
20~40min.
In the step 10, directly cooling temperature is 0~10 DEG C, the ammonium chloride return step three being separated by solid-liquid separation,
Step 7 and step 8 are recycled.
In the step 10, filtrate II I is handled by the way of evaporation and concentration, liquor capacity is original volume after control concentration
0.25~0.4 times, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and step 8 are recycled.
Its chemical component is as follows: sodium paratungstate product after above-mentioned process after testing
It can be seen that sodium paratungstate product obtained by the present invention fully meets the standard of GradeAPT-0 from above-mentioned table.
Example IV
The following steps are included:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, in reverberatory furnace
Interior 600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling first being worn into pulpous state, is then placed in metal trough, is heated after being diluted with water
To boiling, refilters to be made and leach filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 11 with sulfuric acid；By every m3Object
Saturated ammonium chloride and 50 liters of Adlerika are added in feed liquid, stir 3 hours；Again with sulfuric acid tune PH to 10.5；It boils 4 hours, it is quiet
It sets 6 hours；It is filtered, washed with plate and frame filter press, the nonmetallic inclusions such as removal silicon, calcium, phosphorus, boron, carbon, arsenic, removal of impurities filtrate enters
Next program；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: by removing heavy metals filtrate, under condition of heating and stirring, being heated to boiling after sulfuric acid is added, refilter to remove
Molybdenum filtrate；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted, is obtained containing the anti-of tungstic acid in extraction tank
Extract liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, makes sodium tungstate and chlorination
Ammonium sufficiently reacts, and separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: ammonium paratungstate-sodium double salt is mixed with the ammonium chloride solution of predetermined concentration, turns ammonium paratungstate-sodium double salt
Ammonium paratungstate is turned to, and separation of solid and liquid is obtained thick ammonium paratungstate and filtrate II, thick ammonium paratungstate washed using dilute ammonium chloride solution
Completely, ammonium paratungstate is obtained；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride, the carbonic acid using Hou's process for soda production
Sodium may be used as the use of sodium carbonate return step one, and ammonium chloride return step three, step 7 and step 8 are recycled.
In filtrate II when the concentration < 30g/L of NaCl, it is recycled after supplementing ammonium chloride to predetermined concentration into filtrate II；
In filtrate II when concentration >=30g/L of NaCl, filtrate II is merged with filtrate I, enters step in nine and handles together.
In the step 7, the molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4).
In the step 7, sodium tungstate and ammonium chloride reaction process 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.
In the step 8, the mass concentration of ammonium chloride solution is 25%~30%, the ammonium chloride solution and para-tungstic acid
Ammonium-sodium double salt liquid-solid ratio is (4~6): 1.
In the step 8, the temperature that ammonium paratungstate-sodium double salt is converted into ammonium paratungstate is 85~95 DEG C, and transformation time is
20~40min.
In the step 10, directly cooling temperature is 0~10 DEG C, the ammonium chloride return step three being separated by solid-liquid separation,
Step 7 and step 8 are recycled.
In the step 10, filtrate II I is handled by the way of evaporation and concentration, liquor capacity is original volume after control concentration
0.25~0.4 times, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and step 8 are recycled.
Its chemical component is as follows: sodium paratungstate product after above-mentioned process after testing
It can be seen that sodium paratungstate product obtained by the present invention fully meets the standard of GradeAPT-0 from above-mentioned table.
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 technique for preparing ammonium paratungstate with tungsten waste, which comprises the following steps:
One, pretreatment of raw material: tungsten waste and sodium carbonate are mixed by weight the ratio of 1:0.4~1.0, used in reverberatory furnace
600-950 DEG C of temperature sintering, keeps melting or semi-molten state 1~4 hour, agglomeration is come out of the stove；
Two, water logging goes out: sintered material after cooling is first worn into pulpous state, is then placed in metal trough, is heated to boiling after being diluted with water,
It refilters to be made and leaches filtrate；
Three, it cleans: filtrate will be leached and be pumped into removal of impurities bucket, heating stirring adjusts pH value to 8.5-11 with sulfuric acid；By every m3Object
Saturated ammonium chloride and Adlerika 20-50 liter is added in feed liquid, stirs 1.5-3 hours；Again with sulfuric acid tune PH to 8.5-10.5；It boils
Boiling 2-4 hours stands 2-6 hours；It is filtered, washed with plate and frame filter press, removal silicon, calcium, phosphorus, boron, carbon, arsenic etc. are nonmetallic miscellaneous
Matter, removal of impurities filtrate enter next program；
Four, removing heavy metals: vulcanized sodium is added in removal of impurities filtrate, adds sulfuric acid to boil, filters to obtain removing heavy metals filtrate；
Five, it removes molybdenum: removing heavy metals filtrate under condition of heating and stirring, is heated to boiling after sulfuric acid is added, refilter except molybdenum is filtered
Liquid；
Six, acid extract, evaporative crystallization: molybdenum filtrate will be removed, is extracted in extraction tank, obtains the back extraction containing tungstic acid
Liquid；
Seven, double salt: the pH of strip liquor is adjusted to 6.0~7.5 using hydrochloric acid, ammonium chloride is added, fills sodium tungstate and ammonium chloride
Divide reaction, separation of solid and liquid obtains ammonium paratungstate-sodium double salt and filtrate I；
Eight, convert: 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；
Nine, 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；
Ten, 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 9 after filtrate IV is merged with filtrate I and handle together；
11, sodium chloride obtained by step 9 is prepared by sodium carbonate and ammonium chloride using Hou's process for soda production, the sodium carbonate can
For use as the use of sodium carbonate return step one, ammonium chloride return step three, step 7 and step 8 are recycled.
2. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that in the filtrate II
When the concentration < 30g/L of NaCl, it is recycled after supplementing ammonium chloride to predetermined concentration into filtrate II；NaCl's is dense in filtrate II
When degree >=30g/L, filtrate II is merged with filtrate I, enters step in nine and handles together.
3. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 7
In, the molar ratio of sodium tungstate and ammonium chloride is 1:(1.5~4).
4. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 7
In, sodium tungstate and ammonium chloride reaction process are as follows: after chloride solid is added, be stirred to react 0.5 at a temperature of being placed in 50~95 DEG C
Then~3h stands 2~8h of heat preservation at such a temperature.
5. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 8
In, the mass concentration of ammonium chloride solution is 25%~30%.
6. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 8
In, ammonium chloride solution and ammonium paratungstate-sodium double salt liquid-solid ratio are (4~6): 1.
7. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 8
In, the temperature that ammonium paratungstate-sodium double salt is converted into ammonium paratungstate is 85~95 DEG C, and transformation time is 20~40min.
8. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 10
In, directly cooling temperature is 0~10 DEG C, the ammonium chloride return step three being separated by solid-liquid separation, step 7 and step 8 circulation
It uses.
9. the technique according to claim 1 for preparing ammonium paratungstate with tungsten waste, which is characterized in that the step 10
In, filtrate II I is handled by the way of evaporation and concentration, liquor capacity is 0.25~0.4 times of original volume, solid-liquid after control concentration
Isolated ammonium chloride return step three, step 7 and step 8 is recycled.
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| CN115305522A (en) * | 2022-06-20 | 2022-11-08 | 赣州海盛硬质合金有限公司 | Waste hard alloy tungsten resource extraction process and system thereof |
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| 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 |
| 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 |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
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| CN101070188A (en) * | 2007-06-11 | 2007-11-14 | 自贡硬质合金有限责任公司 | Process for producing ammonium paratungstate using tungsten-contained soft waste material |
| 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 |
| 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 |
| CN108557890A (en) * | 2018-05-28 | 2018-09-21 | 中南大学 | A kind of preparation method of ammonium paratungstate |
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| CN115305522A (en) * | 2022-06-20 | 2022-11-08 | 赣州海盛硬质合金有限公司 | Waste hard alloy tungsten resource extraction process and system thereof |
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