CN111097916A - Preparation method of superfine high-purity rhenium powder - Google Patents
Preparation method of superfine high-purity rhenium powder Download PDFInfo
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- CN111097916A CN111097916A CN202010024238.3A CN202010024238A CN111097916A CN 111097916 A CN111097916 A CN 111097916A CN 202010024238 A CN202010024238 A CN 202010024238A CN 111097916 A CN111097916 A CN 111097916A
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
The application relates to a preparation method of superfine high-purity rhenium powder, and belongs to the technical field of rhenium powder. A preparation method of superfine high-purity rhenium powder comprises the following steps: and pre-grinding the rhenium powder at a first ball-milling rotating speed under the condition that a rhenium metal layer exists on the outer surface of the grinding ball and the surface of an inner cavity of the ball-milling tank until the particle size of the rhenium powder reaches 25 micrometers or more and D90 or more and 40 micrometers or less, and then ball-milling the rhenium powder at a second ball-milling rotating speed lower than the first ball-milling rotating speed. The ball milling method can fully grind the rhenium powder, so that the particle size distribution of the rhenium powder is uniform, and the particle size is below 14 mu m. The surfaces of the grinding ball and the ball-milling tank are plated with rhenium metal layers, so that the probability of introducing impurities in the process of ball-milling rhenium powder by a ball-milling device is reduced. The preparation method has high ball milling efficiency and short ball milling process time, and avoids introducing impurities to a greater extent.
Description
Technical Field
The application relates to the technical field of rhenium powder, and in particular relates to a preparation method of superfine high-purity rhenium powder.
Background
Rhenium metal has a relatively high melting point and is a refractory metal. Rhenium is a rare, dispersed element in the crust, with an average estimated to be one billionth of a rare metal. Rhenium has previously been used primarily as a superalloy additive with low requirements for rhenium powder particle size and formability. With the expansion of the application of rhenium metal in recent years, the preparation of rhenium metal products such as rhenium plates, rhenium strips and the like has certain requirements on the quality of rhenium powder.
The metal rhenium powder is prepared by an ammonium rhenate reduction method in common industry, but the rhenium powder prepared by the method has coarse granularity and poor formability. Impurities are easily introduced into the traditional ball milling process, so that the purity of rhenium metal is reduced. At present, the preparation of refractory metal powder by adopting ball milling is reported, but the application of a high-energy ball milling method to the preparation of rhenium powder is not reported. Therefore, the method has important significance for obtaining high-quality rhenium powder.
Disclosure of Invention
Aiming at the defects of the prior art, the embodiment of the application aims to provide a preparation method of superfine high-purity rhenium powder so as to solve the technical problems of coarse particle size and more impurities of the rhenium powder.
In a first aspect, an embodiment of the present application provides a method for preparing ultrafine high-purity rhenium powder, including: and pre-grinding the rhenium powder by adopting a grinding ball and a ball-milling tank at a first ball-milling rotating speed until the granularity of the rhenium powder reaches 25 microns or more and D90 or more and 40 microns or less, and then ball-milling the rhenium powder at a second ball-milling rotating speed lower than the first ball-milling rotating speed.
The rhenium powder grinding method adopts the first ball-milling rotating speed to grind the rhenium raw material until the granularity reaches 25 mu m or less and D90 or less and 40 mu m or less, so that the agglomeration in the rhenium powder is smashed, and then the rhenium powder is further smashed at the lower second ball-milling rotating speed so as to reduce the granularity of the rhenium powder. The ball milling method can fully grind the rhenium powder, so that the particle size distribution of the rhenium powder is uniform, and the particle size is below 14 mu m. The preparation method has high ball milling efficiency and short ball milling process time, and can reduce the introduction of impurities.
In some examples of the application, the grain size of the pre-ground rhenium powder is 30 mu m-D90-35 mu m.
After the pre-grinding, when the particle size of the rhenium powder reaches more than or equal to 30 microns and less than or equal to D90 and less than or equal to 35 microns, the particle size of the rhenium powder is more uniform, and the quality of the rhenium powder obtained by ball milling is higher.
In some embodiments of the present application, the ratio of the first ball milling rotation speed to the second ball milling rotation speed is 3:2 to 8: 3.
The pre-grinding is to break the agglomerates in the rhenium powder at a certain first ball-milling rotating speed, but the first ball-milling rotating speed is not enough to refine the rhenium powder to a finer particle size, and the second ball-milling rotating speed is reduced to levigate the rhenium powder. The inventor of this application discovers through the research, when first ball-milling rotational speed and second ball-milling rotational speed have above-mentioned proportional relation, the ball-milling of assurance pair rhenium powder that can great degree for the rhenium powder particle size after the ball-milling is even, tiny.
In some embodiments of the present application, the step of pre-grinding comprises: and pre-grinding the rhenium powder for 5-10 minutes under the condition that the first ball-milling rotating speed is 300-400r/min, and ball-milling the pre-ground rhenium powder for 20-40 minutes under the condition that the ball-milling rotating speed is 150-200 r/min.
In some embodiments of the present application, the ball milling jar and the milling balls are made of tungsten carbide, and rhenium metal layers are present on the outer surfaces of the milling balls and the inner cavity surfaces of the ball milling jar.
The grinding ball is made of tungsten carbide ball mill with high density and good wear resistance, which is favorable for quickly grinding rhenium powder. The surfaces of the grinding ball and the ball-milling tank are plated with rhenium metal layers, so that the probability of introducing impurities into the ball-milling equipment in the process of ball-milling rhenium powder can be reduced.
The inventor of the application obtains through creative work that the first ball milling rotating speed is 300-type 400r/min, the rhenium powder can be efficiently pre-milled, so that the agglomeration in the rhenium powder is broken, and then the rhenium powder is finely milled at the second ball milling rotating speed of 150-type 200r/min, so that the rhenium powder reaches a certain particle size.
In some embodiments of the present application, the step of pre-grinding the rhenium powder includes: and adding the rhenium-plated grinding ball, the rhenium powder and the ethanol into a rhenium-plated ball-milling tank for pre-milling, wherein the mass ratio of the rhenium-plated grinding ball to the rhenium powder to the ethanol is (20-40) to (2-4).
Rhenium-plated grinding balls, rhenium powder and ethanol can be used for fully ball-milling the rhenium powder in a short time under the matching condition, so that the granularity of the rhenium powder is ensured, and the ball-milling efficiency is improved.
In some embodiments of the present application, the forming of the rhenium metal layer includes: under the condition that the ball milling speed is 280-320r/min, adding grinding balls, rhenium powder and ethanol into a ball milling tank, and carrying out mixing ball milling for 8-24 hours; optionally, the mass ratio of the grinding ball to the rhenium powder to the ethanol is 100 (20-40) to (2-4).
By adopting the method, the rhenium powder can be uniformly plated on the surfaces of the grinding ball and the ball-milling tank, the appearance of the grinding ball is kept, and the rhenium-plated grinding ball and the ball-milling tank cannot fall off to expose tungsten carbide in the subsequent rhenium powder ball-milling process, so that the probability of pollution caused by grinding and crushing of the rhenium powder by the grinding ball is reduced.
In some examples of this application, the feedstock rhenium powder has a particle size of no greater than 150 μm.
The rhenium powder with the particle size can be completely levigated under the pre-grinding and ball-milling conditions, so that the ball-milling efficiency and the ball-milling effect are improved.
In some embodiments of the present application, the method of making further comprises: and drying the ball-milled rhenium powder for 8-24h at the drying temperature of 90-120 ℃.
This application gets rid of the ethanol in the rhenium powder through the stoving for the rhenium powder is granular.
In some embodiments of the present application, the method of making further comprises: carrying out reduction and deoxidation treatment on the dried rhenium powder; optionally, the step of reductive de-oxidation treatment comprises: and (3) keeping the dried rhenium powder in a tubular furnace for 4-8h under the conditions that the treatment atmosphere is hydrogen and the heat preservation temperature is 350-500 ℃.
Through the reduction and deoxidation treatment, the oxygen adsorbed by the rhenium powder in the ball milling thinning process can be removed, and the purity of the rhenium powder is improved.
The beneficial effect of this application includes:
because the post-treatment of the rhenium powder is not separately researched in the prior art, and the traditional ball milling process is poor in rhenium powder grinding effect, the property of a grinding device and the ball milling process are improved by the inventor of the application.
(1) The inventor of the application finds that the density of the rhenium powder and the morphology of the rhenium powder have certain influence on grinding. The inventive research of the inventor of the application shows that the two-step ball milling method is adopted. The agglomeration in the rhenium powder is firstly smashed at the first ball milling rotating speed, the particle size of the rhenium powder is enabled to be more than or equal to 25 mu m and less than or equal to D90 and less than or equal to 40 mu m, and then the rhenium powder is levigated at the second lower ball milling rotating speed. The ball milling method can ensure the ball milling of the rhenium powder to a greater extent, so that the particle size of the rhenium powder after ball milling is uniform and fine.
Further, the rhenium powder is pre-ground for 5-10 minutes under the condition that the first ball-milling rotating speed is 300-400r/min, and in the pre-grinding process under the condition, agglomerates in the rhenium powder are broken through high-speed ball milling to obtain relatively fine rhenium powder. And pre-grinding the rhenium powder until the granularity reaches 25 mu m or more and D90 or more and 40 mu m or less, and ball-milling the pre-ground rhenium powder for 20-40 minutes under the condition that the second ball-milling rotating speed is 150-200 r/min. The ball milling under the condition can be used for fully ball milling the rhenium powder which is easy to sink in the ball milling tank, so that the particle size of the rhenium powder after ball milling is small, and the superfine rhenium powder with the particle size of below 14 mu m is obtained.
(2) The preparation method has high ball milling efficiency, shortens the ball milling time, ensures that the total time of pre-milling and ball milling is not more than one hour, and reduces the probability of introducing impurities.
(3) And the ball milling can and the grinding balls plated with rhenium are adopted for ball milling, so that the ball milling can and the grinding balls are prevented from directly contacting with rhenium powder to introduce impurities. Furthermore, a ball milling tank and a grinding ball made of tungsten carbide material are adopted, and the density of the tungsten carbide material is as high as 15.6g/cm3And the rhenium powder is favorably and rapidly ground. And the rhenium powder is easy to be cold-welded with the tungsten carbide, and a rhenium metal layer can be formed on the ball-milling tank and the milling ball.
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In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a particle size distribution diagram of raw rhenium powder of example 1 of the present application;
FIG. 2 is a graph showing a particle size distribution of ball-milled rhenium powder of example 1 of the present application;
fig. 3 is a particle size distribution diagram of the raw rhenium powder of example 2 of the present application;
FIG. 4 is a graph showing a particle size distribution of ball-milled rhenium powder of example 2 of the present application;
fig. 5 is a scanning electron microscope image of the raw rhenium powder of example 3 of the present application;
FIG. 6 is a scanning electron microscope image of ball-milled rhenium powder of example 3 of the present application;
FIG. 7 is a scanning electron microscope image of the ball-milled rhenium powder of comparative example 4 of the present application;
FIG. 8 is a scanning electron microscope image of the ball-milled rhenium powder of comparative example 5 of the present application;
fig. 9 is a scanning electron microscope image of the ball-milled rhenium powder of comparative example 6 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a method for preparing ultra-fine high-purity rhenium powder according to the embodiments of the present application.
Rhenium metal is a rare dispersion metal, has a rare content in the earth crust and a high price, and limits the application of rhenium element. Rhenium metal is generally used in combination with other metals such as tungsten, nickel, etc., and is less commonly used alone and therefore has been less studied. The conventional rhenium powder is usually prepared by a reduction method, the particle size of the rhenium powder prepared by the method is coarse, and the formability is poor, while the particle size of the rhenium powder can be reduced by the traditional ball-milled rhenium powder, impurities are easily introduced, the purity of the rhenium powder is reduced, and the requirement of high quality cannot be met.
The present inventors have studied rhenium metal in order to improve the quality of rhenium powder and expand the applications of rhenium metal. In the research process, rhenium metal is found to have higher density and other properties different from those of tungsten, nickel and other metals, so that rhenium powder with uniform particle size distribution, fine particle size and good sphericity cannot be obtained by using the traditional grinding method. The inventor of the application obtains a preparation method of superfine high-purity rhenium powder through creative work, and the superfine high-purity rhenium powder can be obtained by adopting an improved ball milling method. Meanwhile, the method shortens the traditional ball milling time and improves the ball milling efficiency of the rhenium powder.
The embodiment of the application provides a preparation method of superfine high-purity rhenium powder, which comprises the following steps: and pre-grinding the rhenium powder by adopting a grinding ball and a ball-milling tank at a first ball-milling rotating speed until the granularity of the rhenium powder reaches 25 microns or more and D90 or more and 40 microns or less, and then ball-milling the rhenium powder at a second ball-milling rotating speed lower than the first ball-milling rotating speed.
Because impurities are easily introduced into the traditional ball milling process, the inventor of the application provides an improvement on ball milling equipment. In the application, the inventor researches the material of the ball mill equipment, and finds that the ball mill equipment is usually made of agate, stainless steel, zirconia and other materials, but because the rhenium powder has high hardness and the alumina has poor wear resistance compared with the rhenium powder, aluminum impurities are easily introduced into the rhenium powder after the rhenium powder is used for a period of time; the low-density zirconium oxide is not fine enough for grinding the rhenium powder, and the rhenium powder with small granularity cannot be obtained; stainless steel introduces a significant amount of iron during the milling process.
The creative research of the inventor of the application proves that the ball mill material made of tungsten carbide has high densityUp to 15.6g/cm3And the rhenium powder is favorably and rapidly ground. And the rhenium powder is easily cold-welded with the tungsten carbide, and the ball mill material is processed, so that a rhenium metal protective layer is cold-welded on the surface of the ball mill material, and impurities are prevented from being introduced due to direct contact of the ball mill material and the rhenium powder. In some embodiments of the present application, the ball milling apparatus comprises a ball milling jar and milling balls. Rhenium metal layers are arranged on the outer surface of the grinding ball and the inner cavity surface of the ball-milling tank.
In one implementation, the step of forming the rhenium metal layer includes: mixing the grinding balls, the rhenium powder and the ethanol in a ball-milling tank under the condition that the ball-milling speed is 280-320r/min, and carrying out ball-milling until the grinding balls and the ball-milling tank are plated with a rhenium metal layer. Alternatively, the mixing and ball milling time is 8-24 hours. The pretreatment under the condition can ensure that the rhenium powder is uniformly plated on the surfaces of the grinding ball and the ball-milling tank, the appearance of the grinding ball is kept, and the rhenium-plated grinding ball and the ball-milling tank cannot fall off to expose tungsten carbide in the subsequent ball-milling process of the rhenium powder, so that the probability of pollution caused by grinding and crushing of the rhenium powder by the grinding ball is reduced. In other embodiments of the present application, a metal layer is plated on the outer surface of the grinding ball and the inner cavity surface of the ball milling tank by using an electrodeposition method, a chemical deposition method, a vacuum ion evaporation method or a magnetron sputtering method. It should be noted that the electrodeposition method, the chemical deposition method, the vacuum ion evaporation or the magnetron sputtering method, and other methods are all general techniques, and the application does not limit the methods.
Further, in the step of plating rhenium on the surface of the ball mill material, the mass ratio of the grinding ball, the rhenium powder and the ethanol is 100 (20-40) to (2-4). The dosage ratio can ensure that the rhenium powder is cold-welded on the surfaces of the grinding ball and the ball-milling tank to a greater extent, and the subsequent ball-milling effect is ensured. Optionally, the mass ratio of the grinding ball to the rhenium powder to the ethanol is 50:10:1, 50:20:1, 25:5:1, 25:10:1, 50:15:1 or 50:15: 2.
Because the prior art does not independently research the post-treatment of the rhenium powder, the traditional ball milling process has poorer effect of grinding the rhenium powder, and the technological parameters of ball milling are the key points of the application. There are many factors that cause poor grinding effect in actual processing, including the strength of the grinding apparatus, the nature of the material being ground, and the grinding process.
The inventor of the application finds that the density of the rhenium powder and the morphology of the rhenium powder have certain influence on grinding. The inventive research of the inventor of the application shows that the two-step wet grinding ball milling method is adopted: the rhenium powder in the ball milling process is subjected to dispersion treatment by adopting ethanol, the rhenium powder is pre-milled at a first ball milling rotating speed under the condition that rhenium metal layers exist on the outer surface of the milling ball and the inner cavity surface of the ball milling tank, the particle size of the rhenium powder is enabled to be more than or equal to 25 microns and less than or equal to D90 and less than or equal to 40 microns, and then the rhenium powder is ball milled at a second ball milling rotating speed lower than the first ball milling rotating speed. This application adopts the ball-milling equipment of tungsten carbide material, and the wearability is good, has "liquid film" protection between ethanol and the ball-milling, reduces the probability of introducing impurity at the ball-milling in-process. To avoid the introduction of impurities, the ethanol in this application is analytically pure anhydrous ethanol.
Because there is the caking in the raw materials rhenium powder, and rhenium powder's density is high, can't carry out abundant crushing to the caking in the rhenium powder if ball-milling speed is not suitable. The inventor of the application finds out through creative work that the ratio of the first ball milling rotating speed to the second ball milling rotating speed is 3:2 to 8: 3. When first ball-milling rotational speed and second ball-milling rotational speed have above-mentioned proportional relation, the ball-milling of assurance pair rhenium powder that can great degree for the rhenium powder particle size after the ball-milling is even, tiny.
Further, rhenium powder, rhenium-plated grinding balls and ethanol are added into a rhenium-plated ball-milling tank, and the rhenium powder is pre-milled for 5-10 minutes under the condition that the first ball-milling rotating speed is 300-400r/min, so that the rhenium powder is milled until the D90 is 25-40 mu m. In the condition pre-grinding process, the agglomerates in the rhenium powder are smashed through high-speed ball milling to obtain relatively fine rhenium powder.
Because the rhenium powder density is big, easily sinks, if grind the rhenium powder with above-mentioned rotational speed always, high-speed ball-milling can't carry out abundant ball-milling to the rhenium powder, leads to the rhenium powder particle size distribution after the ball-milling inhomogeneous. Therefore, the rhenium powder is pre-ground until the granularity reaches 25 mu m or more and D90 or more and 40 mu m or less, and the pre-ground rhenium powder is ball-milled for 20-40 minutes under the condition that the second ball-milling rotating speed is 150-200 r/min. The ball-milling of this condition can carry out abundant ball-milling to the rhenium powder in the ball-milling jar for the rhenium powder particle diameter after the ball-milling is all less, obtains superfine rhenium powder. Furthermore, in order to improve the uniformity of the particle size after ball milling, the pre-milled rhenium powder D90 is 30-35 μm. Alternatively, the pre-milled rhenium powder D90 was 25 μm, 30 μm, 35 μm or 40 μm.
In some embodiments of the present application, the first ball milling speed is 330-. The second ball milling rotation speed is 170-. Optionally, the first ball milling rotation speed is 330r/min, 340r/min, 350r/min, 360r/min or 370r/min, and the second ball milling rotation speed is 170r/min or 180 r/min.
In order to obtain better ball milling effect, the mass ratio of the rhenium-plated grinding balls to the rhenium powder to the ethanol is 100 (20-40) to (2-4). The rhenium-plated grinding ball with the mass ratio can perform sufficient ball milling on rhenium powder within a limited time, the granularity of the rhenium powder is guaranteed, and the ball milling efficiency is improved. The ethanol quantity of this proportion can make the rhenium powder be soaked by ethanol completely, if the ethanol quality is great, makes the rhenium powder concentration in the ethanol reduce, reduces the collision probability between ball-milling and the rhenium powder, reduces the ball-milling effect. Optionally, the rhenium-plated grinding ball, the rhenium powder and the ethanol are in a mass ratio of 50:10:1, 50:20:1, 25:5:1, 25:10:1, 50:15:1 or 50:15: 2.
It should be noted that, in order to obtain the rhenium powder with higher purity, the rhenium powder with high purity of 99.99% is used as a raw material, and in order to improve the efficiency of ball milling, the particle size of the raw material rhenium powder is not more than 150 μm, and the rhenium powder with the particle size can be completely milled under the conditions of the pre-milling and the ball milling. If the particle size of the rhenium powder is larger, the conditions of pre-grinding and ball-milling need to be correspondingly adjusted so as to ensure the ball-milling effect of the rhenium powder.
The preparation method of the superfine high-purity rhenium powder provided by the application adopts a ball milling method, can obtain the superfine high-purity rhenium powder through the improvement of a ball milling process and ball milling materials, shortens the ball milling time, shortens the total time of pre-milling and ball milling to less than one hour, and reduces the probability of introducing impurities.
And after ball milling, keeping the temperature of the rhenium powder for 8-24h at the drying temperature of 90-120 ℃, and removing ethanol in the rhenium powder to enable the rhenium powder to be granular. And after drying, reducing and deoxidizing the dried rhenium powder, removing oxygen adsorbed by the rhenium powder in the process of ball milling thinning, and improving the purity of the rhenium powder. In some embodiments of the present application, the reductive de-oxidation treatment comprises: and (3) keeping the dried rhenium powder in a tubular furnace for 4-8h under the conditions that the treatment atmosphere is hydrogen and the heat preservation temperature is 350-500 ℃. Optionally, the drying temperature is 90 ℃, 100 ℃, 110 ℃ or 120 ℃, and the drying and heat preservation time is 8h, 10h, 15h, 20h or 24 h. The reduction temperature is 350 ℃, 400 ℃, 450 ℃ or 500 ℃, and the reduction heat preservation temperature is 4h, 6h or 8 h.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of superfine high-purity rhenium powder, which comprises the following steps:
high-purity reduced rhenium powder with the purity of 99.99 percent is adopted as a raw material, and D90 is 151 mu m.
Processing rhenium powder by adopting high-energy ball milling, adding 200g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 30g of absolute ethyl alcohol into a rhenium-plated tungsten carbide ball milling tank, then carrying out ball milling for 5 minutes at a rotating speed of 300r/min to grind the rhenium until D90 is 30 mu m, and then carrying out ball milling for 30 minutes at a rotating speed of 200 r/min.
And taking out the rhenium powder, filtering the rhenium powder by using a screen to separate a grinding ball and the rhenium powder, baking the rhenium powder for 8 hours at 100 ℃, crushing the dried rhenium powder by using a shovel, and keeping the temperature for 4 hours in a hydrogen four-tube furnace at the heat preservation temperature of 400 ℃.
The particle size distributions of the raw rhenium powder and the ball-milled rhenium powder were measured by a laser particle sizer, and the results are shown in table 1, fig. 1 and fig. 2. Fig. 1 is a particle size distribution diagram of raw rhenium powder, and fig. 2 is a particle size distribution diagram of ball-milled rhenium powder. As can be seen from the figure, the raw rhenium powder had a non-uniform particle size distribution, large particle sizes and small particle sizes. The curve symmetry of the ball-milled rhenium powder is high, which shows that the particle size uniformity of the ball-milled rhenium powder is improved, and the ball-milled rhenium powder D90 is 13.6 mu m.
Table 1 particle size distribution results
The purities of the raw material rhenium powder and the ball-milled rhenium powder are detected by adopting an inductively coupled plasma mass spectrometry (ICP-MS) method, the purity of the ball-milled rhenium powder is more than or equal to 99.989%, the purity is slightly reduced compared with that of the raw material rhenium powder of 99.998%, and the O content is 0.072%. The impurity components and content results of the ball-milled rhenium powder are shown in the following table:
TABLE 2 impurity analysis Table (wt%)
As can be seen from table 2, the amount of impurities introduced into the ball-milled rhenium powder was very small and the impurity content was low as compared with the raw rhenium powder, which indicates that the ultrafine and high-purity rhenium powder could be obtained by the preparation method of example 1.
Example 2
The embodiment provides a preparation method of superfine high-purity rhenium powder, which comprises the following steps:
high-purity reduced rhenium powder with the purity of 99.99 percent is used as a raw material, and D90 is 77.7 mu m.
Processing rhenium powder by adopting high-energy ball milling, adding 400g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 70g of absolute ethyl alcohol into a rhenium-plated tungsten carbide ball milling tank, then carrying out ball milling for 5 minutes at a rotating speed of 300r/min to grind the rhenium until the D90 is 25 mu m, and then carrying out ball milling for 25 minutes at a rotating speed of 180 r/min.
And taking out the rhenium powder, filtering the rhenium powder by using a screen to separate a grinding ball and the rhenium powder, baking the rhenium powder for 10 hours at 100 ℃, crushing the dried rhenium powder by using a shovel, and keeping the temperature of the dried rhenium powder for 6 hours in a hydrogen four-tube furnace at the heat preservation temperature of 450 ℃.
The particle size distributions of the raw rhenium powder and the ball-milled rhenium powder were measured by a laser particle sizer, and the results are shown in table 3, fig. 3, and fig. 4. Fig. 3 is a particle size distribution diagram of the raw rhenium powder, and fig. 4 is a particle size distribution diagram of the ball-milled rhenium powder. As can be seen from the figure, the raw rhenium powder had a non-uniform particle size distribution, large particle sizes and small particle sizes. The curve symmetry of the ball-milled rhenium powder is high, which shows that the particle size uniformity of the ball-milled rhenium powder is improved, and D90 is 12.3 mu m. The production method of example 2 is explained as being able to obtain ultrafine rhenium powder.
TABLE 3 particle size distribution results
The purities of the raw material rhenium powder and the ball-milled rhenium powder are detected by adopting an ICP-MS method, the purities of the ball-milled rhenium powder are more than or equal to 99.95%, and the O content is 0.088%. It is shown that high purity rhenium powder can be obtained by the preparation method of example 2.
Example 3
The embodiment provides a preparation method of superfine high-purity rhenium powder, which comprises the following steps:
high-purity reduced rhenium powder with the purity of 99.99 percent is used as a raw material, and D90 is 154 mu m.
Processing rhenium powder by adopting high-energy ball milling, adding 300g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 50g of absolute ethyl alcohol into a rhenium-plated tungsten carbide ball milling tank, then carrying out ball milling for 8 minutes at a rotating speed of 400r/min to grind the rhenium until the D90 is 35 mu m, and then carrying out ball milling for 35 minutes at a rotating speed of 200 r/min.
And taking out the rhenium powder, filtering the rhenium powder by using a screen to separate a grinding ball and the rhenium powder, baking the rhenium powder for 12 hours at 100 ℃, crushing the dried rhenium powder by using a shovel, and keeping the temperature of the dried rhenium powder for 8 hours in a hydrogen four-tube furnace at the heat preservation temperature of 500 ℃.
The particle size of the ball-milled rhenium powder is measured by laser particle size, and the ball-milled rhenium powder D90 is 13.3 mu m. And (3) detecting the purity of the ball-milled rhenium powder, wherein the purity is more than or equal to 99.95 percent, and the content of O is 0.079 percent. The preparation method of example 3 is described as being capable of obtaining ultrafine, high-purity rhenium powder.
And (3) detecting microstructures of the raw material rhenium powder and the ball-milled rhenium powder, wherein scanning electron microscope images are shown as fig. 5 and fig. 6. As can be seen from the comparison between fig. 5 and fig. 6, the particle size of the re powder after ball milling is much smaller than that of the raw material re powder, and the re powder after ball milling has uniform particle size and spherical morphology.
Example 4
The present example provides a method for preparing ultra-fine high-purity rhenium powder, which is different from example 1 only in that:
in the ball milling step, 200g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 30g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, then ball milling is carried out for 10 minutes at a rotating speed of 400r/min, the rhenium powder is milled until the D90 is 32 mu m, and then ball milling is carried out for 40 minutes at a rotating speed of 150 r/min.
The particle size of the ball-milled rhenium powder is measured by laser particle size, and the ball-milled rhenium powder D90 is 13.4 mu m. And (3) detecting the purity of the ball-milled rhenium powder, wherein the purity is more than or equal to 99.983%, and the content of O is 0.074%.
Example 5
The present example provides a method for preparing ultra-fine high-purity rhenium powder, which is different from example 1 only in that:
the grinding balls and the ball-milling tank adopted by the ball milling are not plated with metal layers.
The particle size of the ball-milled rhenium powder is measured by laser particle size, and the ball-milled rhenium powder D90 is 13.4 mu m. And (3) detecting the purity of the ball-milled rhenium powder, wherein the purity is more than or equal to 99.63 percent, and the O content is 0.134 percent.
Comparative example 1
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method of the example 1 in that:
in the ball milling step, 200g of rhenium powder, 400g of rhenium-plated tungsten carbide balls and 30g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, then ball milling is carried out for 10 minutes at a rotating speed of 400r/min, rhenium is ground until D90 is 47 mu m, and then ball milling is carried out for 40 minutes at a rotating speed of 150 r/min.
And detecting the particle size distribution of the ball-milled rhenium powder by using a laser particle size analyzer, wherein the ball-milled rhenium powder D90 is 41 mu m. The mass of the grinding balls has a great influence on the ball milling effect, and the ball milling of the rhenium powder is insufficient due to the reduction of the ball milling quality, so that the rhenium powder with large particle size cannot be completely milled.
Comparative example 2
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method of the example 1 in that:
in the ball milling step, 200g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 60g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, then ball milling is carried out for 10 minutes at a rotating speed of 400r/min, rhenium is ground until the D90 is 44 mu m, and then ball milling is carried out for 40 minutes at a rotating speed of 150 r/min.
And detecting the particle size distribution of the ball-milled rhenium powder by using a laser particle size analyzer, wherein the ball-milled rhenium powder D90 is 28 microns. The method has the advantages that the use amount of the ethanol has great influence on the ball milling effect, and the quality of the ethanol is high, so that the rhenium powder in the ethanol is too dispersed, the rhenium powder is not sufficiently milled by the milling ball, and the particle size of the rhenium powder after the ball milling is large.
Comparative example 3
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method of the example 1 in that:
in the ball milling step, a tungsten carbide ball milling tank which is not plated with rhenium and tungsten carbide grinding balls which are not plated with rhenium are adopted to ball mill the rhenium powder.
The purity of the ball-milled rhenium powder is detected by adopting an ICP-MS method, and the impurity components of the raw material rhenium powder are the same as those in the embodiment 1. The purity of the ball-milled rhenium powder is more than or equal to 99.63 percent. The impurity components and content results of the ball-milled rhenium powder are shown in the following table:
TABLE 4 impurity analysis Table (wt%)
| Impurities | Raw rhenium powder | Ball-milling rhenium powder |
| Al | ≤0.0001 | ≤0.0001 |
| Fe | ≤0.0005 | ≤0.0005 |
| Cr | ≤0.0001 | ≤0.0001 |
| Ni | ≤0.0001 | ≤0.0001 |
| Co | ≤0.0001 | ≤0.005 |
| W | ≤0.0005 | ≤0.36 |
| Mo | ≤0.0005 | ≤0.0005 |
| O | 0.085 | 0.134 |
| Re content | ≥99.998％ | ≥99.63％ |
As can be seen from table 4, the rhenium powder after ball milling has a larger amount of impurities than the rhenium powder as the raw material, which indicates that impurities are introduced into the rhenium powder during the ball milling process by the tungsten carbide ball and the tungsten carbide ball mill pot.
Comparative example 4
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method in example 3 in that:
in the ball milling step, rhenium powder is treated by adopting high-energy ball milling, 300g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 50g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, then ball milling is carried out for 4 minutes at a rotating speed of 400r/min, the rhenium is ground until D90 is 50 mu m, and then ball milling is carried out for 35 minutes at a rotating speed of 200 r/min.
SEM of the ball-milled rhenium powder was detected by scanning electron microscopy, and the result is shown in FIG. 7. Fig. 7 shows that the particle size distribution of the ball-milled rhenium powder is not uniform, indicating that the rhenium powder was not sufficiently ball-milled during the second ball-milling.
Comparative example 5
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method in example 3 in that:
in the ball milling step, rhenium powder is treated by adopting high-energy ball milling, 300g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 50g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, and then ball milling is carried out for 43 minutes at a rotating speed of 200 r/min.
The particle size of the ball-milled rhenium powder was measured by scanning electron microscopy, and the results are shown in fig. 8. Fig. 8 shows that the particle size distribution of the rhenium powder after ball milling is not uniform, and the particle size is large, which indicates that the rhenium powder cannot be better ball-milled at the ball milling speed, and cannot be finely milled, resulting in a large particle size of the rhenium powder.
Comparative example 6
The comparative example provides a preparation method of superfine high-purity rhenium powder, and the method is only different from the method in example 3 in that:
in the ball milling step, rhenium powder is treated by adopting high-energy ball milling, 300g of rhenium powder, 1000g of rhenium-plated tungsten carbide balls and 50g of absolute ethyl alcohol are added into a rhenium-plated tungsten carbide ball milling tank, and then ball milling is carried out for 43 minutes at a rotating speed of 500 r/min.
The particle size of the ball-milled rhenium powder was measured by scanning electron microscopy, and the results are shown in fig. 9. Fig. 9 shows that the particle size distribution of the ball-milled rhenium powder is not uniform, and the particle size is larger, which indicates that the rhenium powder cannot be sufficiently ball-milled at a higher ball-milling speed, so that the rhenium powder with a large particle size cannot be milled, and a small part of the rhenium powder is milled, resulting in a larger particle size distribution range of the rhenium powder.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A preparation method of superfine high-purity rhenium powder is characterized by comprising the following steps: and pre-grinding rhenium powder by adopting a grinding ball and a ball-milling tank at a first ball-milling rotating speed until the particle size of the rhenium powder reaches 25 microns or more and D90 or more and 40 microns or less, and then ball-milling the rhenium powder at a second ball-milling rotating speed lower than the first ball-milling rotating speed.
2. The method for preparing the superfine high-purity rhenium powder as claimed in claim 1, wherein the particle size of the pre-ground rhenium powder is more than or equal to 30 μm and less than or equal to D90 and less than or equal to 35 μm.
3. The method for preparing the ultrafine high-purity rhenium powder according to claim 1, wherein the ratio of the first ball milling rotation speed to the second ball milling rotation speed is 3:2 to 8: 3.
4. The method for preparing the ultrafine high-purity rhenium powder as claimed in claim 3, wherein the rhenium powder is pre-ground for 5-10 minutes under the condition that the first ball-milling rotation speed is 300-400r/min, and after the pre-grinding, the rhenium powder subjected to the pre-grinding is ball-milled for 20-40 minutes under the condition that the second ball-milling rotation speed is 150-200 r/min.
5. The method for preparing superfine high-purity rhenium powder according to any one of claims 1 to 4, wherein the step of pre-grinding the rhenium powder comprises the following steps: and adding the rhenium-plated grinding ball, the rhenium powder and ethanol into a rhenium-plated ball-milling tank for pre-milling, wherein the mass ratio of the rhenium-plated grinding ball to the rhenium powder to the ethanol is (20-40) to (2-4).
6. The method for preparing the superfine and high-purity rhenium powder as claimed in claim 1, wherein the ball-milling tank and the milling balls are made of tungsten carbide, and rhenium metal layers are arranged on the outer surfaces of the milling balls and the surfaces of inner cavities of the ball-milling tank.
7. The method for preparing ultra-fine high-purity rhenium powder as claimed in claim 1 or 6, wherein the step of forming the rhenium metal layer comprises: under the condition that the ball milling speed is 280-320r/min, adding grinding balls, rhenium powder and ethanol into a ball milling tank, and carrying out mixing ball milling for 8-24 hours; optionally, the mass ratio of the grinding balls to the rhenium powder to the ethanol is 100 (20-40) to (2-4).
8. The method for preparing superfine high-purity rhenium powder according to claim 1, wherein the particle size of the raw rhenium powder is not more than 150 μm.
9. The method for preparing ultra-fine high-purity rhenium powder as claimed in any one of claims 1 to 4, wherein the method further comprises: and drying the ball-milled rhenium powder for 8-24h at the drying temperature of 90-120 ℃.
10. The method for preparing ultra-fine high-purity rhenium powder according to claim 9, further comprising the following steps: carrying out reduction and deoxidation treatment on the dried rhenium powder;
optionally, the step of reductive de-oxidation treatment comprises: and (3) preserving the heat of the dried rhenium powder for 4-8h in a tubular furnace under the conditions that the treatment atmosphere is hydrogen and the heat preservation temperature is 350-500 ℃.
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