CN106044857B - A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution - Google Patents
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution Download PDFInfo
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- CN106044857B CN106044857B CN201610621914.9A CN201610621914A CN106044857B CN 106044857 B CN106044857 B CN 106044857B CN 201610621914 A CN201610621914 A CN 201610621914A CN 106044857 B CN106044857 B CN 106044857B
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Abstract
The invention discloses a kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, ammonium tungstate solution is first passed through to nitrogen to be pre-processed, composite reactive reagent is added again, it is stirred with graphite stirring rod, stage cools, obtained order of ammoniumparatungstate crystal purity is small compared with high, particle diameter, with regular hexahedron crystalline texture, WO3, the impurity such as Mo, As it is few, with significant social and economic benefits.
Description
Technical field
The present invention relates to a kind of method for separating ammonium paratungstate, more particularly to one kind separating-purifying in ammonium tungstate solution are secondary
The method of ammonium tungstate.
Background technology
Ammonium paratungstate (APT) is the important intermediate compound for producing tungsten powder, tungsten filament, tungsten-bast alloy and all tungsten materials, is also
Large exporting of China.Due to genetic affinity, APT crystal property such as crystal morphology, lattice parameter, particle mean size and grain
Degree distribution, loose specific weight and mobility influence very big to the material property of follow-up powder metallurgy product tungsten powder, tungsten filament and tungsten alloy,
The thus exploitation of High Performance W material, to from solution crystalline product be APT granularity, loose ratio, mobility, crystal morphology and crystalline substance
The characteristics such as lattice parameter propose higher and higher requirement.Especially it is worthy of note that, the tungsten that high homogeneity monocrystalline APT powders are produced
Powder is few due to the defect of material, and compacted density is high, is the excellent material for producing high temperature resistance, sag resistance, Resisting fractre, shock resistance tungsten filament
Material.Main application fields are high-performance, heavy alloy and antidetonation tungsten filament, and the product such as miniature drill.
In ammonium paratungstate (APT) production technology, WO in APT crystalline mother solutions (ammonium tungstate solution)3Content typically constitutes from mistake entirely
The 5%~15% of journey, additionally containing impurity such as Mo, P, As, it is more that existing crystallization obtains impurity in ammonium paratungstate product, purity
Not high, granularity is larger.
The content of the invention
It is it is an object of the invention to provide a kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, ammonium tungstate is molten
Liquid is first passed through nitrogen and pre-processed, then adds composite reactive reagent, is stirred with graphite stirring rod, stage cooling, and what is obtained is secondary
Ammonium tungstate crystal purity is small compared with high, particle diameter, and with regular hexahedron crystalline texture, and impurity is few.
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 8-
Filtered after 10h, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.3-1.7, water
Bath is heated to 70-80 DEG C, stirs 50-70 minutes, obtains composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 50-150r/min, drop
Temperature separated out crystallization to holding after 40-50 DEG C 30-50 minutes, and filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 20-30 DEG C, kept for 10-30 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces regular hexahedron crystalline texture, and purity is more than 98% secondary tungsten
Sour ammonium.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14.2-
14.7:5.5-6.5。
A diameter of 1-5cm of described graphite stirring rod.
Described ammonium tungstate solution is wolframite gained after alkali soluble, ion exchange impurity and purification transition, consisting of：
WO370-80g/L, Cl-2.0-3.0mol/L, contains Mo, Si, P, As impurity.
The advantage of the invention is that：
1st, first ammonium tungstate solution is pre-processed, nitrogen is passed through into solution under the conditions of lucifuge, secondary tungsten can be improved
Sour ammonium purity and effectively go the removal of impurity.
2nd, composite reactive reagent is added in the solution, the particle size of crystal is controlled, and obtains the crystallization of regular hexahedron,
Meet the requirement to ammonium paratungstate product granularity.
3rd, it is stirred in crystallization process with graphite stirring rod, partial impurities and composite reactive examination in ammonium tungstate solution
After material chelating in agent, it can adsorb on graphite stirring rod, substantially reduce the impurity of product.
4th, join under pretreatment, composite reactive reagent, graphite stirring rod coupling, having abandoned the technique of routine
Number, the technique for devising stage cooling improves crystallization effect, the ammonium paratungstate product particle epigranular of generation, with rule
Hexahedron crystallization shape, percent crystallization in massecuite is more than 97%, and impurity is few, meets the demand of subsequent applications.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 8h
After filter, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.3, water-bath adds
Heat stirs 50 minutes to 70 DEG C, obtains composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 50r/min, is cooled to
Kept for 30 minutes after 40 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 20 DEG C, kept for 10 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces the ammonium paratungstate of regular hexahedron crystallization.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14.2:
5.5。
A diameter of 1-5cm of described graphite stirring rod.
Described ammonium tungstate solution is wolframite gained after alkali soluble, ion exchange impurity and purification transition, consisting of：
Every liter contains WO370-80g, Cl-2.0-3.0mol/L, Mo, Si, P, As impurity are micro.
Remaining be the same as Example 1.
Embodiment 2：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 9h
After filter, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.5, water-bath adds
Heat stirs 60 minutes to 75 DEG C, obtains composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 100r/min, cooling
Kept for 40 minutes after to 45 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 25 DEG C, kept for 20 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces the ammonium paratungstate of regular hexahedron crystallization.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14.5:
6。
Remaining be the same as Example 1.
Embodiment 3：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 9h
After filter, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.6, water-bath adds
Heat stirs 70 minutes to 70 DEG C, obtains composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 80r/min, is cooled to
Kept for 40 minutes after 50 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 25 DEG C, kept for 20 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces the ammonium paratungstate of regular hexahedron crystallization.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14.6:
6.2。
Remaining be the same as Example 1.
Embodiment 4：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 10h
After filter, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.7, water-bath adds
Heat stirs 50-70 minutes to 80 DEG C, obtains composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 150r/min, cooling
Kept for 50 minutes after to 50 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 30 DEG C, kept for 30 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces the ammonium paratungstate of regular hexahedron crystallization.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14.7:
6.5。
Remaining be the same as Example 1.
Comparative example 1：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, while being passed through nitrogen in the solution, keep 6h
After filter, obtain filtrate；
(2) addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1, heating water bath
To 80 DEG C, stir 90 minutes, obtain composite solution；
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 200r/min, cooling
Kept for 20 minutes after to 60 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
(4) continue filtrate a to be cooled to 40 DEG C, kept for 5 minutes, separate out crystallization, filtering must crystallize b；
(5) crystallization a and crystallization b are merged, drying produces the ammonium paratungstate of regular hexahedron crystallization.
Described composite reactive reagent be DTAC, octodecyl betaine mixing and
Into dodecyl sulphate ethanolamine salt, DTAC, the mass ratio of alkyl dimethyl betaine are 14:5.
Remaining be the same as Example 1.
Comparative example 2：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
Same as Example 1, difference is：
(1) ammonium tungstate solution is placed in open-top receptacle, be placed at lucifuge, kept filtering after 8h, obtain filtrate；
Comparative example 3：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
Same as Example 2, difference is：
Described composite reactive reagent is that dodecyl sulphate ethanolamine salt, alkyl dimethyl betaine are mixed,
Dodecyl sulphate ethanolamine salt, the mass ratio of alkyl dimethyl betaine are 14.5:6.
Comparative example 4：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
Same as Example 3, difference is：
(3) composite solution is cooled after stirring, stirred in cooling, rotating speed is 80r/min, and 40 are kept after being cooled to 50 DEG C
Minute, crystallization is separated out, filtering must crystallize a and filtrate a；
Comparative example 5：
A kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, is concretely comprised the following steps：
Same as Example 4, difference is：
(3) composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 150r/min, cooling
Kept for 50 minutes after to 50 DEG C, separate out crystallization, filtering must be crystallized and filtrate；
(4) crystallization is dried, produces the ammonium paratungstate of regular hexahedron crystallization.
The effect for the ammonium para-tungstate crystal that each embodiment and comparative example separating-purifying are obtained is as follows
Shown in table：
The effect for the ammonium para-tungstate crystal that embodiments of the invention 1-4 separating-purifyings are obtained is can be seen that from upper table data
Better than comparative example 1 (technological parameter not within the scope of the present invention), comparative example 2 (not using the pretreating process for being passed through nitrogen),
Comparative example 3 (composite reactive reagent is different), comparative example 4 (not using graphite stirring rod), comparative example 5 (not cooled using the stage),
It can be seen that the present invention is stirred rod using the pretreating process of nitrogen, addition composite reactive reagent, with graphite, cool with the stage
Technique is combined, and isolated ammonium paratungstate purity is high, and granularity is small, WO3, the impurity such as Mo, As it is few, with significant society, economic
Benefit.
Claims (3)
1. a kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution, it is characterized in that：Concretely comprise the following steps：
（1）Ammonium tungstate solution is placed in open-top receptacle, is placed at lucifuge, while being passed through nitrogen in the solution, is kept after 8-10h
Filtering, obtains filtrate；
（2）Addition composite reactive reagent in filtrate, the mass ratio of filtrate and composite reactive reagent is 10:1.3-1.7, water-bath adds
Heat stirs 50-70 minutes to 70-80 DEG C, obtains composite solution；
（3）Composite solution is cooled after stirring, stirred in cooling with graphite stirring rod, rotating speed is 50-150 r/min, cooling
Kept for 30-50 minutes after to 40-50 DEG C, separate out crystallization, filtering must crystallize a and filtrate a；
（4）Continue filtrate a to be cooled to 20-30 DEG C, kept for 10-30 minutes, separate out crystallization, filtering must crystallize b；
（5）Crystallization a and crystallization b are merged, drying produces regular hexahedron crystalline texture, and purity is more than 98% ammonium paratungstate；
Composite reactive reagent is DTAC, octodecyl betaine is mixed, dodecyl
Trimethyl ammonium chloride, the mass ratio of alkyl dimethyl betaine are 14.2-14.7:5.5-6.5.
2. a kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution as claimed in claim 1, it is characterized in that：Graphite
A diameter of 1-5cm of stirring rod.
3. a kind of method of the separating-purifying ammonium paratungstate in ammonium tungstate solution as claimed in claim 1, it is characterized in that：Wolframic acid
Ammonium salt solution is wolframite gained after alkali soluble, ion exchange impurity and purification transition, consisting of： WO3 70-80g/L, Cl-
2.0-3.0 mol/L, contain Mo, Si, P, As impurity.
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| CN106564955A (en) * | 2016-11-02 | 2017-04-19 | 崇义章源钨业股份有限公司 | Method of preparing superfine APT |
| CN116495784B (en) * | 2023-06-20 | 2023-09-15 | 赣州市海龙钨钼有限公司 | Method for purifying ammonium paratungstate in ammonium tungstate solution |
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| CN103739016B (en) * | 2013-12-25 | 2016-06-29 | 崇义章源钨业股份有限公司 | The method processing thick ammonium tungstate solution |
| CN105197997B (en) * | 2015-09-11 | 2017-01-04 | 中国有色集团（广西）平桂飞碟股份有限公司 | The method of ammonium paratungstate degree of depth clarification |
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