CN113816429B - Method for coarsening particles of ammonium paratungstate - Google Patents
Method for coarsening particles of ammonium paratungstate Download PDFInfo
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- CN113816429B CN113816429B CN202111337375.3A CN202111337375A CN113816429B CN 113816429 B CN113816429 B CN 113816429B CN 202111337375 A CN202111337375 A CN 202111337375A CN 113816429 B CN113816429 B CN 113816429B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of wet metallurgy, and particularly relates to a particle coarsening method and purification of ammonium paratungstate. The invention discovers that pure water, an ammonia water solution with a certain concentration or an ammonium salt solution is added into the ammonium paratungstate with smaller granularity, so that the ammonium paratungstate with smaller granularity can be converted into the ammonium paratungstate product with larger granularity, and the impurity content of the product can be reduced. By utilizing the technical scheme of the invention, for the same production line of a tungsten hydrometallurgy plant, an ammonium paratungstate product with larger granularity can be conveniently and quickly selected and prepared according to actual needs. The invention has short process flow, no equipment requirement, simple operation method, no need of expensive chemical reagent and very low cost.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy, and particularly relates to a particle coarsening method of ammonium paratungstate.
Background
In recent years, cemented carbides are being developed in both ultra-fine and ultra-coarse directions. The coarse grain hard alloy has special performance and application, particularly has a series of advantages of less structural defects, high microhardness, small microstrain and the like at high temperature, is widely applied to wear-resistant structural members such as rock drilling tools, stamping dies, cold heading dies, high-speed wire rollers and the like, and is widely applied to marketThe demand is vigorous. Ammonium paratungstate is a main intermediate product for preparing tungsten powder and other products of hard alloy and the like. In the production process, the appearance and the particle size distribution of the ammonium paratungstate are found to have strong correlation with the appearance and the particle size distribution of the tungsten powder, namely the ammonium paratungstate has heredity. Ammonium Paratungstate (APT) medium temperature reduction for preparing coarse-crystal tungsten powder, published in superhard materials engineering, takes ammonium paratungstate as a raw material, adds an additive, and reduces under the wet hydrogen condition of 1000 ℃ to prepare the coarse-crystal tungsten powder. However, it is more convenient to directly prepare the ammonium paratungstate product with larger particle size according to the 'hereditary' principle of particle size. Chinese tungsten industry published in the article of research on continuous crystallization process for preparing coarse-grained ammonium paratungstate, continuous evaporative crystallization process is adopted to research more coarse-grained APT product, and emptying interval time, steam pressure and WO in ammonium tungstate solution are examined ３ The influence of factors such as concentration, stirring speed and the like on physical properties such as the granularity of the APT product. However, the process is complicated, the parameters to be regulated and controlled are large, and APT prepared by other methods (such as a discontinuous method) must be re-dissolved to obtain ammonium tungstate solution and then recrystallized, which brings huge pressure to the production process.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a particle size coarsening method which is simple to operate and has extremely low cost aiming at the ammonium paratungstate product with smaller particle size produced in the hydrometallurgy process.
In order to solve the above technical problems, the present invention provides the following technical solutions.
A method for coarsening particles of ammonium paratungstate comprises the steps of adding ammonium paratungstate with smaller particle size into a reaction tank, and then adding NH 4 + Ammonia water or ammonium salt solution with the concentration of 0.5-20g/L is stirred at low speed for a period of time at high temperature, and then the ammonium paratungstate product with larger granularity is obtained.
Further preferably, the temperature range of the high temperature is 90-150 ℃.
More preferably, the ammonium paratungstate is suspended by stirring at a low speed.
More preferably, the ammonium salt is one or more selected from ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium bisulfate, ammonium chloride, and ammonium nitrate.
Further preferably, the solid content of the reaction system is 100 to 2000g/L.
More preferably, the reaction time is 0.5 to 10 hours.
Further, after the reaction was completed, the material was cooled to room temperature and then filtered and washed.
The present invention further unexpectedly found that the aqueous ammonia or ammonium salt solutions described above can be replaced with water.
The invention further unexpectedly discovers that the technical scheme can further reduce the impurity content in the ammonium paratungstate product while coarsening the ammonium paratungstate particles.
Further, the ammonium paratungstate with the smaller particle size is ammonium paratungstate decahydrate and/or ammonium paratungstate tetrahydrate.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The ammonium paratungstate product with smaller granularity can be prepared without re-dissolving to obtain ammonium tungstate solution and then recrystallizing to obtain the ammonium paratungstate product with larger granularity. For a tungsten hydrometallurgy plant, under the condition of the same production line, the ammonium paratungstate product with larger granularity can be conveniently and rapidly selected and prepared according to actual needs.
(2) By adopting the technical scheme provided by the invention, the ammonium paratungstate product particles can be coarsened, and the contents of impurities such as K, na, P and the like in the ammonium paratungstate product can be effectively reduced.
(3) Short process flow, no equipment requirement, simple operation method, no need of expensive chemical reagents and very low cost.
Drawings
FIG. 1 is a graph showing the particle size distribution of ammonium paratungstate decahydrate prepared by crystallization in a hydrometallurgical plant for tungsten in the Jiangxi province.
FIG. 2 is a particle size distribution plot of the coarsened ammonium paratungstate product of example 1.
FIG. 3 is a particle size distribution plot of the coarsened ammonium paratungstate product of example 2.
FIG. 4 is a particle size distribution plot of the coarsened ammonium paratungstate product of example 3.
Detailed Description
The invention is described in detail below, and the description in this section is merely exemplary and explanatory and should not be construed as limiting the scope of the invention in any way.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
In the examples of the present invention, ammonium paratungstate decahydrate, which had a particle size D50 of 36.98. Mu.m, a K content of 12ppm, a Na content of 5ppm and a P content of 15ppm and was prepared by crystallization in a hydrometallurgical plant of tungsten in Jiangxi, was used as a treatment target.
Selecting NH in the process of coarsening the ammonium paratungstate decahydrate 4 + 0.5-20g/L ammonia water or ammonium salt solution or pure water, the temperature is selected to be 90-150 ℃, the solid content is 100-2000g/L, and the ammonium paratungstate is in a suspension state by low-speed stirring, so that the product particles can be coarsened, and the product impurities can be reduced.
Ammonium paratungstate decahydrate is easily converted into ammonium paratungstate tetrahydrate when being heated, and the scheme can also be utilized to coarsen product particles and reduce impurities in the product.
Several specific examples are selected below for the description.
Example 1
50g of the above ammonium paratungstate was charged into a 250mL reaction tank, followed by 100mL of NH 4 + Heating and stirring are started for an ammonia water solution with the concentration of 2g/L, the heating is carried out until the temperature is 90 ℃, and the stirring speed is 10rpm when the ammonium paratungstate is basically in a suspension state. And after stirring for 3 hours, stopping stirring, cooling to room temperature, filtering and washing to obtain an ammonium paratungstate product.
The particle size analysis of the obtained ammonium paratungstate product is shown in fig. 2. As can be seen from FIG. 2, the particle size D50 of the resulting ammonium paratungstate product was 245.3. Mu.m. Simultaneously, the impurity content in the product is detected, and the result is as follows: the K content was 8ppm, the Na content was 4ppm and the P content was 5ppm.
Example 2
The present embodiment differs from embodiment 1 in that: (1) Addition of NH 4 + Ammonium bicarbonate solution with concentration of 10g/L instead of ammonia solution; (2) the reaction temperature was 130 ℃.
The ammonium paratungstate product obtained in example 2 was analytically tested for particle size distribution, and as a result, as shown in FIG. 3, D50 was 70.80. Mu.m. Continuously detecting the impurity content in the product, wherein the result is as follows: the K content was 5ppm, the Na content was 2ppm and the P content was 5ppm.
Example 3
The present embodiment differs from embodiment 1 in that: (1) adding pure water instead of the aqueous ammonia solution; (2) the reaction temperature was 110 ℃.
The particle size distribution of the ammonium paratungstate product obtained in example 3 was analytically tested, and as a result, as shown in FIG. 4, the D50 of the product was 252.0. Mu.m. The impurity content in the product is detected, and the result is as follows: the K content was 7ppm, the Na content was 3ppm and the P content was 5ppm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for coarsening particles of ammonium paratungstate is characterized in that ammonium paratungstate with smaller particle size is added into a reaction tank, and then NH is added 4 + Ammonia water or ammonium salt solution with the concentration of 0.5-20g/L is stirred for a period of time at a low speed at a high temperature, and then an ammonium paratungstate product with larger granularity is obtained; the high temperature range is 90-150 ℃; stirring at low speed to make ammonium paratungstate in suspension state.
2. The method for coarsening particles of ammonium paratungstate according to claim 1, wherein the ammonium salt is one or more selected from ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium bisulfate, ammonium chloride, and ammonium nitrate.
3. The method for coarsening particles of ammonium paratungstate according to claim 1, wherein the solid content of the system is 100 to 2000g/L.
4. The method for coarsening particles of ammonium paratungstate according to claim 1, wherein the time is 0.5 to 10 hours.
5. The method for coarsening particles of ammonium paratungstate according to any one of claims 1 to 4, wherein water is used instead of ammonia water or the ammonium salt solution.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5761632A (en) * | 1980-10-02 | 1982-04-14 | Toshiba Corp | Production of crude particles of ammonium paratungstenate crystal |
| US5125964A (en) * | 1990-09-10 | 1992-06-30 | General Electric Company | Fluidized bed process for preparing tungsten powder |
| US5578285A (en) * | 1994-12-20 | 1996-11-26 | Osram Sylvania Inc. | Process for reducing the average particle size of ammonium paratungstate powders |
| CN1286732C (en) * | 2004-11-11 | 2006-11-29 | 北京科技大学 | Preparation for nanometer anhydrous wolframic acid powder |
| DE102007005287B4 (en) * | 2007-02-02 | 2009-10-01 | H.C. Starck Gmbh | Process for the preparation of ammonium paratungstate tetrahydrate and high purity ammonium paratungstate tetrahydrate |
| DE102007005286B4 (en) * | 2007-02-02 | 2009-08-27 | H.C. Starck Gmbh | Process for the preparation of ammonium paratungstate hydrates and ammonium paratungstate decahydrate |
| CN101182039A (en) * | 2007-12-07 | 2008-05-21 | 金堆城钼业股份有限公司 | Crystallization method of ammonium paratungstate |
| CN102485380B (en) * | 2010-12-06 | 2013-06-19 | 北京有色金属研究总院 | Preparation method of submicron nearly spherical tungsten powder |
| CN112299486A (en) * | 2020-11-03 | 2021-02-02 | 江钨世泰科钨品有限公司 | High-purity ultra-coarse particle ammonium paratungstate and preparation method thereof |
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