CN114515835B - Molybdenum powder and preparation method thereof - Google Patents
Molybdenum powder and preparation method thereof Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 160
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims description 68
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 10
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000011946 reduction process Methods 0.000 description 13
- 238000011068 loading method Methods 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides molybdenum powder and a preparation method thereof, comprising the following steps: step 1, adding water accounting for 0-10% of the mass of molybdenum dioxide into molybdenum dioxide powder to obtain water-containing molybdenum dioxide powder; and step 2, gradually adding the aqueous molybdenum dioxide powder to 950-1050 ℃ in a hydrogen atmosphere to obtain the reduced molybdenum powder. The invention eliminates a great amount of molybdenum powder polymers and the influence on the growth of molybdenum powder particles caused by the great amount of rapid formation of molybdenum powder crystal nucleus when molybdenum dioxide is reduced in a strong reducing atmosphere, and effectively controls the distribution of molybdenum powder particle size, so that the shape and the particle size distribution of the molybdenum powder are more beneficial to the forming and sintering process.
Description
Technical Field
The invention belongs to the field of metallurgy, and relates to molybdenum powder and a preparation method thereof.
Background
In the molybdenum metal processing deformation process, molybdenum processing technological parameters and quality mainly depend on the density, hardness, grain number and metal gap impurity elements of a molybdenum sintered blank, the density, hardness, grain number and gap impurity elements of the molybdenum sintered blank are mainly determined by the Fisher particle size, particle size distribution, specific surface area, molybdenum powder morphology and the size of the gap element oxygen content of molybdenum powder, and the molybdenum powder is mainly prepared by high-purity molybdenum oxide hydrogen reduction, so that the size of the oxygen content is the most important gap impurity influenced by the molybdenum processing process.
At present, the most main method for preparing the domestic molybdenum powder is high-purity molybdenum trioxide, and the molybdenum powder is prepared by a high-purity hydrogen two-time reduction method. The technological process is that the first reduction is carried out at 350-650 ℃, and molybdenum trioxide is reduced into molybdenum dioxide under the condition of hydrogen; the second reduction is carried out to reduce the molybdenum dioxide into molybdenum powder under the condition of hydrogen at the temperature of more than 650 ℃, and the reaction is as follows:
MoO 3(s) +H 2(g) →MoO 2(s) +H 2 O (g) (1)
MoO 2(s) +2H 2 →Mo (s) +2H 2 O (g) (2)
the molybdenum powder is directly reduced into molybdenum powder by hydrogen, and for the purposes that the reaction of the equations (1) and (2) is complete and the operation process of the reaction process is safe, the hydrogen consumption is more than 10 times than the actual consumption, so that the reactions of the equations (1) and (2) are carried out under the condition of absolute excess hydrogen, the water vapor generated by the reaction is rapidly removed along with the hydrogen, the reaction of the equation (2) is particularly increased along with the gradual temperature rise, the reaction speed is also increased, the reaction of the equation (2) can only carry out the reaction in the forward direction, the influence of the reverse reaction relative to the forward reaction is almost negligible, the reverse reaction conditions of molybdenum powder crystal nucleus generation and growth in the molybdenum powder reduction process are broken, so that the molybdenum dioxide hydrogen is reduced into a large number of crystal nuclei, the crystal nuclei cannot grow up, finally, the agglomeration of molybdenum powder is formed, the growth of molybdenum powder crystal grains and the distribution range of molybdenum powder particles are deteriorated and destroyed, the molybdenum powder particles are easily agglomerated and agglomerated molybdenum powder is not beneficial to gas discharge during sintering, so that the sintering density is not beneficial to the sintering molding in the later stage.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the molybdenum powder and the preparation method thereof, which eliminate the influence on the growth of molybdenum powder particles and the occurrence of a large number of molybdenum powder polymers caused by the rapid formation of a large number of molybdenum powder crystal nuclei when molybdenum dioxide is reduced in a strong reducing atmosphere, and effectively control the distribution of the molybdenum powder particle size, so that the shape and the particle size distribution of the molybdenum powder are more beneficial to the forming and sintering process.
The invention is realized by the following technical scheme:
a preparation method of molybdenum powder comprises the following steps:
step 1, adding water accounting for 0-10% of the mass of molybdenum dioxide into molybdenum dioxide powder to obtain water-containing molybdenum dioxide powder;
and step 2, gradually heating the water-containing molybdenum dioxide powder to 950-1050 ℃ in a hydrogen atmosphere to obtain reduced molybdenum powder.
Preferably, in the step 1, the addition amount of water is 5% -8% of the mass of the molybdenum dioxide.
Preferably, in step 1, water is sprayed into the molybdenum dioxide powder by atomization.
Preferably, in step 1, the preparation method of the molybdenum dioxide powder comprises the following steps: the molybdenum trioxide calcined by ammonium dimolybdate is used as an initial raw material and is obtained by hydrogen reduction, and the dew point of the adopted hydrogen is between +35 ℃ and +45 ℃.
Preferably, in the step 1, the specific surface area of the molybdenum dioxide powder is 0.20-0.25 m 2 /g。
Preferably, the step 2 specifically comprises: taking a reduction furnace tube as a reactor, wherein the temperature of the reduction furnace tube gradually rises from one end to the other end, the temperature of the low-temperature end of the reduction furnace tube is 650 ℃, and the temperature of the high-temperature end of the reduction furnace tube is 950-1050 ℃; introducing hydrogen into the reduction furnace tube, adding the water-containing molybdenum dioxide powder into the low-temperature end of the reduction furnace tube, gradually moving towards the high-temperature end of the reduction furnace tube, and obtaining a product of the high-temperature end of the reduction furnace tube, namely the reduction molybdenum powder.
Preferably, the molybdenum dioxide powder stays in the reduction furnace tube for 7 hours.
Preferably, in the step 2, the reduced molybdenum powder is sieved by a 200-mesh sieve to obtain molybdenum powder.
Further, the specific surface area of the obtained molybdenum powder is 0.15-0.32 m 2 /g, fisher average particle size 2.5-4.5 um.
The molybdenum powder obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the molybdenum powder of the invention increases the temperature of the raw materials to 950 ℃ to 1050 ℃ at most. According to research, the temperature of 920 ℃ is the crystal phase transition temperature of molybdenum powder, when the temperature of the reduction process is less than 920 ℃, the morphology of molybdenum powder prepared by reduction inherits the morphology of precursor molybdenum dioxide, the molybdenum powder is in a monoclinic tetragonal crystal form, when the temperature of the molybdenum powder reduction process is greater than 920 ℃, the morphology of molybdenum powder prepared by hydrogen reduction is in an ellipsoidal shape, and when the temperature of the molybdenum powder reduction process is at 920 ℃, the morphology of molybdenum powder prepared by hydrogen reduction is in an ellipsoidal shape, but a very small part of molybdenum powder is not completely converted into an ellipsoidal tetragonal columnar crystal form. In industrial production practice, the ellipsoidal molybdenum powder has better effect in profiling and sintering compared with the molybdenum powder with other two morphologies, so that the maximum reduction temperature is set to 950-1050 ℃, the ellipsoidal molybdenum powder can be obtained, and the subsequent processing and forming are facilitated. On the other hand, in the molybdenum dioxide reduction process, in order to ensure the control of the molybdenum crystal nucleus generation rate, an atomization method is adopted to uniformly spray part of water, so that the sufficient oxidation capability is ensured under the strong reducing atmosphere of the molybdenum dioxide hydrogen reduction, the reverse reaction of the formula (2) can be performed to a certain extent, the molybdenum powder crystal nucleus generation rate is controlled, the influence on the growth of molybdenum powder particles and the occurrence of a large amount of agglomerates in the molybdenum powder caused by the large amount and rapid formation of the molybdenum powder crystal nucleus when the molybdenum dioxide is reduced under the strong reducing atmosphere are eliminated, meanwhile, the particle size distribution of the molybdenum powder is effectively controlled, the obtained molybdenum powder does not have agglomerates, the gas is discharged during sintering, and the morphology and the particle size distribution of the obtained molybdenum powder are more favorable for the forming and sintering processes.
Furthermore, in the molybdenum trioxide reduction process, the reverse reaction of the formula (1) can be performed to a certain extent by adopting hydrogen with high dew point, and the molybdenum dioxide obtained by reduction has no agglomeration phenomenon.
Drawings
FIG. 1 shows MoO in a thermogravimetric analyzer (TGA) 3 The precursor reduces SEM of molybdenum dioxide under the condition of hydrogen; a is MoO obtained in experiment 1 2 A crystal nucleus aggregate; b is MoO obtained in experiment 2 2 ；
FIG. 2 shows MoO in a thermogravimetric analyzer (TGA) 2 SEM of molybdenum powder is generated in the hydrogen reduction process; a is the appearance of molybdenum powder prepared at the temperature of less than 920 ℃ in experiment 3; b is the appearance of molybdenum powder prepared in experiment 4 at a temperature of more than 920 ℃; c is the appearance of molybdenum powder prepared at 920 ℃ in experiment 5;
FIG. 3 SEM of molybdenum powder prepared in example 1;
FIG. 4 SEM of molybdenum powder prepared in example 2;
fig. 5 SEM of the molybdenum powder prepared in example 3.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
In order to find and solve the process control method and process parameters of molybdenum powder particle morphology, size and particle size distribution range in the molybdenum powder generation process, the invention simulates the industrial production process on a thermogravimetric analyzer to find an effective, simple and easy-to-operate method.
The thermogravimetric analyzer experiment process is as follows:
experiment 1
Adding high-purity molybdenum trioxide prepared by decomposing ammonium dimolybdate as an initial raw material into a thermogravimetric analyzer, introducing hydrogen with a dew point of-60 ℃, gradually heating to 550 ℃, and reducing the molybdenum trioxide into molybdenum dioxide powder at 350-550 ℃, wherein SEM is shown in figure 1a.
Experiment 2
Adding high-purity molybdenum trioxide prepared by decomposing ammonium dimolybdate as an initial raw material into a thermogravimetric analyzer, introducing hydrogen with a dew point of +45 ℃, gradually heating to 550 ℃, and reducing the molybdenum trioxide into molybdenum dioxide powder at 350-550 ℃, wherein SEM is shown in figure 1 b.
Experiment 3
The molybdenum dioxide obtained in experiment 2 is added into a thermogravimetric analyzer, hydrogen with the dew point of minus 60 ℃ is introduced, the temperature is gradually increased to 910 ℃, the molybdenum dioxide is reduced into molybdenum powder at 650-910 ℃, and the SEM is shown in figure 2 a.
Experiment 4
The molybdenum dioxide obtained in experiment 2 is added into a thermogravimetric analyzer, hydrogen with the dew point of +35 ℃ is introduced, the temperature is gradually increased to 950 ℃, the molybdenum dioxide is reduced into molybdenum powder at 650-950 ℃, and the SEM is shown in figure 2 b.
Experiment 5
The molybdenum dioxide obtained in experiment 2 is added into a thermogravimetric analyzer, hydrogen with the dew point of +35 ℃ is introduced, the temperature is gradually increased to 920 ℃, the molybdenum dioxide is reduced into molybdenum powder at 650-920 ℃, and the SEM is shown in figure 2 c.
The following is the experimental result of simulated molybdenum powder hydrogen reduction by the thermogravimetric analyzer:
in the primary reduction process of experiment 1 and experiment 2, the experimental process parameters are the same except the dew point of hydrogen, molybdenum dioxide obtained by reduction in hydrogen with the dew point of +45 ℃ in experiment 2 has no agglomeration phenomenon, as shown in fig. 1b, and molybdenum dioxide obtained by reduction in hydrogen with the dew point of-60 ℃ in experiment 1 has serious agglomeration phenomenon, as shown in fig. 1a. Moreover, as can be seen from fig. 1, in the preparation of molybdenum dioxide powder by one-time hydrogen reduction using high-purity molybdenum trioxide prepared by decomposing ammonium dimolybdate as an initial raw material as a precursor, molybdenum dioxide inherits the crystal form of the molybdenum trioxide precursor, and molybdenum trioxide inherits the lamellar morphology feature of monoclinic tetragonal ammonium dimolybdate.
In the secondary reduction process of experiments 3-5, the experimental process parameters are the same except that the reduction temperature and the hydrogen dew point are different. As can be seen from fig. 2, in the preparation of molybdenum powder by secondary hydrogen reduction, when the temperature in the reduction process is less than 920 ℃, the morphology of the molybdenum powder prepared by reduction inherits the morphology of the precursor molybdenum dioxide, and the crystal form of the molybdenum dioxide precursor inherits the monoclinic tetragonal crystal form of the initial raw material ammonium dimolybdate, so that the morphology of the reduced molybdenum powder is tetragonal, as shown in fig. 2 a; when the temperature of the molybdenum powder reduction process is higher than 920 ℃, the morphology of the molybdenum powder prepared by hydrogen reduction is ellipsoidal, as shown in fig. 2 b; when the temperature of the molybdenum powder reduction process is 920 ℃, the morphology of the molybdenum powder prepared by hydrogen reduction is ellipsoidal, but a very small part of the molybdenum powder is not completely converted into an ellipsoidal tetragonal columnar crystal form, as shown in figure 2 c. From fig. 2a and 2b, it can also be seen that the molybdenum powder obtained from different hydrogen dew points has different particle sizes, and at the same time, the oxygen content of the molybdenum powder is less than 1500ppm at the temperature of 950 ℃ in experiment 4.
According to the thermal gravimetric analysis experimental result and the industrial production practice, the one-time reduction molybdenum dioxide morphology is better than that of the one-time reduction molybdenum dioxide morphology shown in FIG. 1b and FIG. 1a, and the specific surface of the laser particle size analyzer is not more than 0.35m 2 Preferably 0.2 to 0.25m 2 /g; the secondary reduced molybdenum powder is sequenced from poor to good according to the using effect of compression molding and sintering: FIG. 2-a < FIG. 2-c < FIG. 2-b.
Therefore, in the molybdenum powder reduction process, the size and the particle size distribution of the molybdenum powder can be controlled by the amount of steam in the reduction furnace, and the morphology of the product can be controlled by the reduction temperature.
According to studies, it was found that controlling the amount of water by the dew point of hydrogen causes inaccurate water control due to the condensation problem of water, because it is performed by adding water to molybdenum dioxide in the later actual production.
According to the research results, the preparation method of the final molybdenum powder comprises the following steps:
step 1, uniformly spraying pure water accounting for 0 to 10 wt% (preferably 5 to 8 wt%) of the mass of molybdenum dioxide into molybdenum dioxide powder by adopting an atomization method to obtain water-containing molybdenum dioxide powder; the Specific Surface Area (SSA) of the molybdenum dioxide is not more than 0.35m 2 Preferably 0.20 to 0.25m 2 /g；
Step 2, introducing hydrogen into a reduction furnace tube, loading the water-containing molybdenum dioxide powder obtained in the step 1 into a magnetic boat, adding a low-temperature end of the reduction furnace tube, moving towards a high-temperature end of the reduction furnace tube at a certain speed, reducing molybdenum dioxide in a hydrogen reduction atmosphere, and sieving the obtained product with a 200-mesh sieve to obtain molybdenum powder; the temperature in the reduction furnace tube gradually rises from one end to the other end, the temperature of the low temperature end of the reduction furnace tube is 650 ℃, and the temperature of the high temperature end is 950-1050 ℃;
the hydrogen flow in the reducing furnace tube is 20-25 Nm 3 /h; 2.0 kg/boat of molybdenum dioxide; reduction rate: 2 boat/30-35 min, the specific surface area of the obtained molybdenum powder is 0.15-0.32 m 2 /g, fisher average particle size 2.5-4.5 um. The residence time of the magnetic boat from the reduction furnace tube was 7 hours.
The molybdenum dioxide powder is obtained by taking ammonium dimolybdate calcined molybdenum trioxide as an initial raw material and reducing the initial raw material by hydrogen, wherein the adopted hydrogen dew point is between +35 ℃ and +45 ℃.
Example 1
In the embodiment, molybdenum trioxide roasted by ammonium dimolybdate is taken as an initial raw material, molybdenum dioxide is taken as a precursor for molybdenum powder reduction, and a hydrogen reduction method is adopted to produce molybdenum powder.
Step 1, uniformly spraying pure water accounting for 5% of the mass of molybdenum dioxide into molybdenum dioxide powder by adopting an atomization method to obtain water-containing molybdenum dioxide powder; the specific surface area of the molybdenum dioxide is 0.20 to 0.25m 2 /g；
Step 2, the flow rate of the reduction furnace tube is 20-25 Nm 3 Hydrogen per hour, loading the water-containing molybdenum dioxide powder obtained in the step 1 into a magnetic boat according to the boat loading amount of 2.0 kg/boat, adding the low-temperature end of a reduction furnace tube, moving the magnetic boat towards the high-temperature end of the reduction furnace tube at a certain speed, keeping the magnetic boat in the reduction furnace tube for 7 hours, loading the magnetic boat at the speed of 2 boat/30-35 min, reducing the molybdenum dioxide under the hydrogen reducing atmosphere, and sieving the obtained product with a 200-mesh sieve to obtain molybdenum powder; the temperature of the reducing furnace is gradually increased from one end to the other end, the temperature of the low-temperature end of the reducing furnace tube is 650 ℃, and the temperature of the high-temperature end is 1050 ℃.
The molybdenum powder obtained in this example has a Fisher average particle size of 2.5-3.5 um, a Bulk Density (Bulk Density): 1.2g/cm 3 Tap density (determined by mixing time): TD > 3.0g/cm 3 Laser particle size distribution d10=3.5 to 5.5, d50=10 to 25, d90=20 to 25, specific Surface Area (SSA) 0.32m 2 And/g, the oxygen content of the molybdenum powder at the front of the furnace is less than 800PPm, and the shape of the molybdenum powder is ellipsoidal, as shown in figure 3.
The special molybdenum powder mainly used for the domestic magnetron molybdenum cap is obtained in the embodiment.
Example 2
Step 1, uniformly spraying pure water accounting for 8% of the mass of molybdenum dioxide into molybdenum dioxide powder by adopting an atomization method to obtain water-containing molybdenum dioxide powder; the specific surface area of the molybdenum dioxide is 0.20 to 0.25m 2 /g；
Step 2, the flow rate of the reduction furnace tube is 20-25 Nm 3 Hydrogen per hour, loading the water-containing molybdenum dioxide powder obtained in the step 1 into a magnetic boat according to the boat loading amount of 2.0 kg/boat, adding the low-temperature end of a reduction furnace tube, moving the magnetic boat towards the high-temperature end of the reduction furnace tube at a certain speed, keeping the magnetic boat in the reduction furnace tube for 7 hours, loading the magnetic boat at the speed of 2 boat/30-35 min, reducing the molybdenum dioxide under the hydrogen reducing atmosphere, and sieving the obtained product with a 200-mesh sieve to obtain molybdenum powder; the temperature of the reducing furnace is gradually increased from one end to the other end, the temperature of the low-temperature end of the reducing furnace tube is 650 ℃, and the temperature of the high-temperature end is 1050 ℃.
The molybdenum powder obtained in this example has a Fisher average particle size of 4.2 to 4.5um, a Bulk Density (Bulk Density): 1.2g to 1.3g/cm 3 The particle size distribution (determined by mixing time), d10=5 to 10, d50=10 to 25, d90=40 to 45, specific Surface Area (SSA) 0.15 to 0.23m 2 And/g, the oxygen content of the molybdenum powder in the front of the furnace is less than 800PPm, and the shape of the molybdenum powder is elliptic, as shown in figure 4. The water content of this example is greater than that of example 1, and the Fisher average particle size of the molybdenum powder obtained increases.
The special molybdenum powder mainly used for the high-grade pure molybdenum plate and the special-shaped piece is obtained in the embodiment.
Example 3
Step 1, uniformly spraying pure water accounting for 10% of the mass of molybdenum dioxide into molybdenum dioxide powder by adopting an atomization method to obtain water-containing molybdenum dioxide powder; the specific surface area of the molybdenum dioxide is 0.20 to 0.25m 2 /g；
Step 2, the flow rate of the reduction furnace tube is 20-25 Nm 3 Hydrogen per hour, loading the water-containing molybdenum dioxide powder obtained in the step 1 into a magnetic boat according to the boat loading amount of 2.0 kg/boat, adding the low-temperature end of a reduction furnace tube, moving the magnetic boat towards the high-temperature end of the reduction furnace tube at a certain speed, keeping the magnetic boat in the reduction furnace tube for 7 hours, loading the magnetic boat at the speed of 2 boat/30-35 min, reducing the molybdenum dioxide under the hydrogen reducing atmosphere, and sieving the obtained product with a 200-mesh sieve to obtain molybdenum powder; the temperature of the reducing furnace is gradually increased from one end to the other end, the temperature of the low-temperature end of the reducing furnace tube is 650 ℃, and the temperature of the high-temperature end is 1050 ℃.
The molybdenum powder obtained in this example has a Fisher average particle size of 2.5-3.0 um, a Bulk Density (Bulk Density): 1.2g/cm 3 Since the molybdenum dioxide is added with excessive pure water, the reverse reaction speed of the reduction of the molybdenum dioxide is enhanced, the growth of molybdenum powder particles is reduced, as shown in fig. 5, the reaction is performed, and in severe cases, the reaction cannot be completely or the generation of the clamping occurs.
The present embodiment is only for illustrating the method of the present invention, and is not limited to the process and parameter ranges related to the method, and other modifications and equivalent substitutions of the present invention by workers skilled in the art should be included in the scope of the patent claims of the present invention without departing from the spirit scope of the present invention.
Claims (6)
1. The preparation method of the molybdenum powder is characterized by comprising the following steps:
step 1, adding water accounting for 5% -8% of the mass of molybdenum dioxide into molybdenum dioxide powder to obtain water-containing molybdenum dioxide powder;
step 2, gradually heating the water-containing molybdenum dioxide powder to 950-1050 ℃ in a hydrogen atmosphere to obtain reduced molybdenum powder;
in the step 1, the preparation method of the molybdenum dioxide powder comprises the following steps: the molybdenum trioxide roasted by ammonium dimolybdate is taken as an initial raw material, and is obtained by hydrogen reduction, wherein the dew point of the adopted hydrogen is between +35 ℃ and +45 ℃;
in the step 1, spraying water into molybdenum dioxide powder by adopting an atomization method;
in the step 1, the specific surface area of the molybdenum dioxide powder is 0.20-0.25 m 2 /g。
2. The method for preparing molybdenum powder according to claim 1, wherein step 2 specifically comprises: taking a reduction furnace tube as a reactor, wherein the temperature of the reduction furnace tube gradually rises from one end to the other end, the temperature of the low-temperature end of the reduction furnace tube is 650 ℃, and the temperature of the high-temperature end of the reduction furnace tube is 950-1050 ℃; introducing hydrogen into the reduction furnace tube, adding the water-containing molybdenum dioxide powder into the low-temperature end of the reduction furnace tube, gradually moving towards the high-temperature end of the reduction furnace tube, and obtaining a product of the high-temperature end of the reduction furnace tube, namely the reduction molybdenum powder.
3. The method for producing molybdenum powder according to claim 2, wherein the residence time of the molybdenum dioxide powder in the reduction furnace tube is 7 hours.
4. The method for preparing molybdenum powder according to claim 1, wherein in step 2, the reduced molybdenum powder is sieved through a 200-mesh sieve to obtain molybdenum powder.
5. The method for preparing molybdenum powder according to claim 4, wherein the specific surface area of the obtained molybdenum powder is 0.15-0.32 m 2 /g, fisher average particle size 2.5-4.5 um.
6. Molybdenum powder obtained by the process of any one of claims 1-5.
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