CN103286317B - Method for preparing molybdenum powder by ammonium molybdate - Google Patents
Method for preparing molybdenum powder by ammonium molybdate Download PDFInfo
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- CN103286317B CN103286317B CN201310270901.8A CN201310270901A CN103286317B CN 103286317 B CN103286317 B CN 103286317B CN 201310270901 A CN201310270901 A CN 201310270901A CN 103286317 B CN103286317 B CN 103286317B
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Abstract
The invention provides a method for preparing molybdenum powder by ammonium molybdate. The method includes the steps: firstly, screening the ammonium molybdate by a 40-mesh screen to obtain an oversize product and placing the screened oversize product into a ball mill for ball-milling to obtain ammonium molybdate powder; secondly, performing primary hydrogen reduction treatment for the ammonium molybdate powder by the aid of a primary reduction furnace in hydrogen atmosphere to obtain molybdenum dioxide; thirdly, performing secondary hydrogen reduction treatment for the molybdenum dioxide by the aid of a secondary reduction furnace in the hydrogen atmosphere to obtain rough molybdenum powder; and fourthly, placing the screened rough molybdenum powder into a mixer for uniform mixing to obtain finished molybdenum powder. Preparation technology is simple, and the method is safe, reliable and suitable for industrialized mass production. The molybdenum powder prepared by the method can meet technical requirements of a national standard GB/T3461-2006, and can be widely used for preparing raw materials for molybdenum and molybdenum alloy products such as molybdenum slabs, molybdenum bars, molybdenum piercing mandrels and molybdenum fabricated parts.
Description
Technical field
The invention belongs to rare metal powder metallurgical technology, be specifically related to a kind of method utilizing ammonium molybdate to prepare molybdenum powder.
Background technology
In industrial processes, be raw material with industrial molybdenum oxide usually, adopt ammonia leaching successively, acid method that is heavy and crystallization prepares ammonium molybdate.Because ammonium molybdate has the physical characteristic of easy deliquescence, easily caking, therefore need ammonium molybdate to carry out process of sieving, in industrial processes, generally ammonium molybdate is crossed 40 mesh sieves.
Ammonium molybdate being crossed the screenings after 40 mesh sieves is without deliquescence, crystalline solid without caking, low, the white fluffy of moisture content, can be widely used in petroleum refining catalyst field and the fertilizer industries such as hydrodesulfurization, and be typically used as the raw material preparing high-quality molybdenum powder.And ammonium molybdate is crossed the oversize after 40 mesh sieves due to the crystallization water more, lump serious and hard, color distortion is obvious, has had a strong impact on the subsequent production of molybdenum product.This oversize conveniently technique can not prepare high-quality molybdenum powder, main cause has two, usually rotary pipe type reduction furnace is adopted to prepare molybdenum powder in first industrial processes, because rotary pipe type reduction furnace adopts the feeding manner of spiral charging, and ammonium molybdate cross 40 mesh sieves after oversize cause the damage of equipment because larger blocky-shaped particle usually blocks feeding screw, cause parturient paresis; Even if it two is adopt pusher multi-tube furnace, because the particle diameter of this oversize is excessive, and make the core of particle hard due to the existence of mass crystallization water and free water, hydrogen reduction can not fully be reacted, cause oxygen in made molybdenum powder, potassium, sodium equal size severe overweight, the technical requirement of molybdenum converted products can not be met.
The method generally adopted in current industrial production is that the oversize after ammonium molybdate is crossed 40 mesh sieves returns in production of molybdic ammonium line and re-starts the heavy and crystallization treatment of ammonia leaching, acid, causes the increase of energy consumption and the rising of cost thus.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of method utilizing ammonium molybdate to prepare molybdenum powder.Adopt the molybdenum powder prepared of the method to be up to state standards the technical requirement of GB/T3461-2006, the raw material of the molybdenums such as preparation molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods can be used as.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method utilizing ammonium molybdate to prepare molybdenum powder, and it is characterized in that, the method comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; The time of a described hydrogen reducing process is 5h ~ 6h, and the flow velocity of described hydrogen is 10m/s ~ 15m/s, and the dew point of described hydrogen is-70 DEG C ~-60 DEG C; A described hydrogen reducing process adopts four-temperature region or five warm areas reduction system, when adopting four-temperature region reduction system, the temperature of each warm area is followed successively by: 500 DEG C, 535 DEG C, 570 DEG C and 600 DEG C, and when employing five warm area reduction system, the temperature of each warm area is followed successively by 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; The time of described secondary hydrogen reduction treatment is 6.5h ~ 7.5h, and the flow velocity of described hydrogen is 20m/s ~ 30m/s, and the dew point of described hydrogen is-75 DEG C ~-65 DEG C; Described secondary hydrogen reduction treatment adopts three-temperature-zone, five warm areas or six warm areas reduction system, when adopting three-temperature-zone reduction system, the temperature of each warm area is followed successively by 880 DEG C, 930 DEG C and 980 DEG C, when employing five warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 905 DEG C, 930 DEG C, 955 DEG C and 980 DEG C, and when employing six warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C and 980 DEG C;
Step 4, molybdenum powder rough described in step 3 is crossed 160 order ~ 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, it is characterized in that, in ammonium molybdate powder described in step one, the mass percentage of molybdenum is not less than 54%; The moisture content of described ammonium molybdate powder is 3% ~ 5%.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, is characterized in that, the Fisher particle size of ammonium molybdate powder described in step one is 6.0 μm ~ 22.0 μm, and the apparent density of described ammonium molybdate powder is 1.0g/cm
3~ 1.5g/cm
3.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, it is characterized in that, ball mill described in step one is ASM type Horizontal stirring ball mill, ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum ball, in described molybdenum ball, the mass percentage of molybdenum is not less than 99.95%, and the diameter of described molybdenum ball is 8mm ~ 12mm.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, it is characterized in that, described in step 2, a reduction furnace is rotary pipe type reduction furnace; The stove of secondary reduction described in step 3 is pusher 18 pipe furnaces.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, is characterized in that, the Fisher particle size of finished product molybdenum powder described in step 4 is 2.0 μm ~ 5.0 μm, and the apparent density of described finished product molybdenum powder is 0.8g/cm
3~ 1.2g/cm
3.
A kind of above-mentioned method utilizing ammonium molybdate to prepare molybdenum powder, it is characterized in that, in finished product molybdenum powder described in step 4, the mass percentage of molybdenum is not less than 99.9%.
The present invention adopts ammonium molybdate to be raw material, and the method through twice hydrogen reducing prepares molybdenum powder.Wherein, the temperature of a hydrogen reducing is set in 500 DEG C within the scope of 600 DEG C by the present invention, and adopt four-temperature region or five warm areas reduction system, when adopting four-temperature region reduction system, the temperature of each warm area is followed successively by: 500 DEG C, 535 DEG C, 570 DEG C and 600 DEG C, and when employing five warm area reduction system, the temperature of each warm area is followed successively by 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C.This is because ammonium molybdate first pyrolysis in this temperature range becomes molybdenum trioxide, and molybdenum trioxide is molybdenum dioxide by hydrogen reducing again.If the temperature of a hydrogen reducing is too low, multiple unstable mesophase spherule can be generated as (NH)
4mo
14o
43, (NH)
2mo
14o
43, MoO
2.8and Mo
4o
11, cause can not get target product molybdenum dioxide or molybdenum dioxide low yield; If the temperature of a hydrogen reducing is too high, ammonium molybdate and pyrogenous origin molybdenum trioxide thereof can be made to volatilize in a large number, cause raw material heavy losses, and localized hyperthermia can generate and is difficult to be caused by the fused mass of hydrogen reducing " stifled stove " phenomenon, finally make to contain a large amount of metal " speck " in finished product molybdenum powder, have a strong impact on product quality.And, the present invention adopts three-temperature-zone, five warm areas or six warm areas reduction system to secondary hydrogen reduction treatment, when adopting three-temperature-zone reduction system, the temperature of each warm area is followed successively by 880 DEG C, 930 DEG C and 980 DEG C, when employing five warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 905 DEG C, 930 DEG C, 955 DEG C and 980 DEG C, and when employing six warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C and 980 DEG C.If this is because the temperature of secondary hydrogen reduction is too low, can cause not carrying out secondary hydrogen reduction reaction or sluggish because of heat energy, have a strong impact on production smooth, efficiently carry out; If the temperature of secondary hydrogen reduction is too high, made metal molybdenum and low-melting impurities can be made to form the eutectic of metal grain state, and caking is serious, can not obtain even-grained molybdenum powder.And, also remarkable impact is there is in the warm area that a hydrogen reducing and secondary hydrogen reduce system of reducing on molybdenum powder quality, according to single warm area reduction system, then made metal molybdenum and low-melting impurities can be made to form eutectic and produce caking phenomenon owing to there is localized hyperthermia, or because heat energy causes sluggish and " not saturating " not, the caking phenomenon that same generation is serious.If the time of a hydrogen reducing or secondary hydrogen reduction is too short, then reduction reaction can be made insufficient, a large amount of intermediate product remains; If the overlong time of a hydrogen reducing or secondary hydrogen reduction, then can form the eutectic of metallic state, can not obtain even-grained molybdenum powder.In addition, the too low meeting of flow velocity of hydrogen causes reduction reaction insufficient, and reacted material blows back again and cause the pollution of material and the confusion of operation to unreacted material by the too high meeting of hydrogen flow rate; The too high meeting of dew point of hydrogen causes moisture content in hydrogen high, not only can not take away the moisture in raw material, also can bring more juicy on the contrary, product is lumpd serious; Dew point of hydrogen is too high, causes the increase of cost because gas obtains not easily.The present invention is by large quantity research, finally four-temperature region or five warm areas reduction system are adopted to a hydrogen reducing, three-temperature-zone, five warm areas or six warm areas reduction system are adopted to secondary hydrogen reduction, and select the time of a hydrogen reducing process to be 5h ~ 6h, hydrogen flow rate is 10m/s ~ 15m/s, and dew point of hydrogen is-70 DEG C ~-60 DEG C; The time of secondary hydrogen reduction treatment is 6.5h ~ 7.5h, and hydrogen flow rate is 20m/s ~ 30m/s, and dew point of hydrogen is-75 DEG C ~-65 DEG C.
The present invention compared with prior art has the following advantages:
(1) first ammonium molybdate is crossed 40 mesh sieves and is got oversize by the present invention, again this oversize is carried out ball mill crushing and obtain ammonium molybdate powder, then ammonium molybdate powder is directly carried out twice hydrogen reducing process and obtain high-quality molybdenum powder, abandoned traditional handicraft completely and this oversize need have been returned the tediously long operation that production of molybdic ammonium line re-starts the heavy and crystallization treatment of ammonia leaching, acid; The present invention is by large quantity research, finally four-temperature region or five warm areas reduction system are all adopted to a hydrogen reducing, three-temperature-zone, five warm areas or six warm areas reduction system are adopted to secondary hydrogen reduction, and select the time of a hydrogen reducing process to be 5.0h ~ 6.0h, hydrogen flow rate is 10m/s ~ 15m/s, and dew point of hydrogen is-70 DEG C ~-60 DEG C; The time of secondary hydrogen reduction treatment is 6.5h ~ 7.5h, and hydrogen flow rate is 20m/s ~ 30m/s, and dew point of hydrogen is-75 DEG C ~-65 DEG C; The technological parameter adopted all is better than general Mo powder production, control range is narrow and precision is high, from the moisture content removed to the full extent ammonium molybdate powder, and the moisture generated in twice hydrogen reducing reaction, fully ensure that normally carrying out of twice reduction reaction, finally obtain high-quality molybdenum powder;
(2) the present invention is accurately controlled by the technological parameter reduced to a hydrogen reducing and secondary hydrogen, ammonium molybdate is crossed the oversize after 40 mesh sieves directly to carry out twice hydrogen reducing process and can obtain high-quality molybdenum powder, the present invention has significant energy-saving and cost-reducing effect to the processing method of this oversize compared with traditional treatment method, and production cost is significantly reduced;
(3) the molybdenum powder epigranular adopting the present invention to prepare, solid colour, good dispersion, reunites few, chemical composition meets the technical requirement of standard GB/T/T3461-2006, can be used as the raw material of the molybdenums such as preparation molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods;
(4) preparation technology of the present invention is simple, safe and reliable, is applicable to industrialized mass production.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 1.
Fig. 2 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 2.
Fig. 3 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 3.
Fig. 4 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 4.
Fig. 5 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 5.
Fig. 6 is the microscopic appearance SEM photo of molybdenum powder prepared by the embodiment of the present invention 6.
Detailed description of the invention
Embodiment 1
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.95%, and diameter is the molybdenum ball of 10mm; The Fisher particle size of described ammonium molybdate powder is 16.0 μm, and the apparent density of described ammonium molybdate powder is 1.3g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.4%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 3.2%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts four-temperature region reduction system, detailed process is: first all heated by four of rotary pipe type reduction furnace warm areas, make each warm area temperature be followed successively by 500 DEG C, 535 DEG C, 570 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-64 DEG C and regulate the flow velocity of hydrogen to be 13m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 5.5h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts three-temperature-zone reduction system, detailed process is: first all heated by three warm areas of pusher 18 pipe furnaces, make each warm area temperature be followed successively by 880 DEG C, 930 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-68 DEG C and regulate the flow velocity of hydrogen to be 28m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 7h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 1, the epigranular of finished product molybdenum powder as seen from Figure 1, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 3.0 μm, and apparent density is 0.9g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.92%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
Embodiment 2
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.96%, and diameter is the molybdenum ball of 10mm; The Fisher particle size of described ammonium molybdate powder is 9.0 μm, and the apparent density of described ammonium molybdate powder is 1.2g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.3%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 3.9%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts five warm area reduction systems, detailed process is: first all heated by five of rotary pipe type reduction furnace warm areas, make each warm area temperature be followed successively by 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-70 DEG C and regulate the flow velocity of hydrogen to be 15m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 5h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts five warm area reduction systems, detailed process is: first all heated by five warm areas of pusher 18 pipe furnaces, make each warm area temperature be followed successively by 880 DEG C, 905 DEG C, 930 DEG C, 955 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-65 DEG C and regulate the flow velocity of hydrogen to be 30m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 6.5h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 160 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 2, the epigranular of finished product molybdenum powder as seen from Figure 2, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 3.2 μm, and apparent density is 1.0g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.92%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
Embodiment 3
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.97%, and diameter is the molybdenum ball of 10mm; The Fisher particle size of described ammonium molybdate powder is 6.0 μm, and the apparent density of described ammonium molybdate powder is 1.0g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.8%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 3%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts five warm area reduction systems, detailed process is: first all heated by five of rotary pipe type reduction furnace warm areas, make each warm area temperature be followed successively by 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-60 DEG C and regulate the flow velocity of hydrogen to be 10m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 6h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts six warm area reduction systems, detailed process is: first all heated by six warm areas of pusher 18 pipe furnaces, make each warm area temperature be followed successively by 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-65 DEG C and regulate the flow velocity of hydrogen to be 20m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 7.5h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 3, the epigranular of finished product molybdenum powder as seen from Figure 3, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 4.8 μm, and apparent density is 1.2g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.95%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
Embodiment 4
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.96%, and diameter is the molybdenum ball of 10mm; The Fisher particle size of described ammonium molybdate powder is 15.0 μm, and the apparent density of described ammonium molybdate powder is 1.4g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.6%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 3.8%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts four-temperature region reduction system, detailed process is: first all heated by four of rotary pipe type reduction furnace warm areas, make each warm area temperature be followed successively by 500 DEG C, 535 DEG C, 570 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-65 DEG C and regulate the flow velocity of hydrogen to be 12m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 5.5h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts five warm area reduction systems, detailed process is: first all heated by five warm areas of pusher 18 pipe furnaces, make each warm area temperature be followed successively by 880 DEG C, 905 DEG C, 930 DEG C, 955 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-70 DEG C and regulate the flow velocity of hydrogen to be 25m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 7h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 4, the epigranular of finished product molybdenum powder as seen from Figure 4, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 2.0 μm, and apparent density is 0.8g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.92%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
Embodiment 5
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.95%, and diameter is the molybdenum ball of 8mm; The Fisher particle size of described ammonium molybdate powder is 22.0 μm, and the apparent density of described ammonium molybdate powder is 1.5g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.9%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 5.0%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts five warm area reduction systems, detailed process is: first all heated by five of rotary pipe type reduction furnace warm areas, make each warm area temperature be respectively 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-60 DEG C and regulate the flow velocity of hydrogen to be 10m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 6h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts three-temperature-zone reduction system, detailed process is: first all heated by three warm areas of pusher 18 pipe furnaces, make each warm area temperature be respectively 880 DEG C, 930 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-65 DEG C and regulate the flow velocity of hydrogen to be 30m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 6.5h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 5, the epigranular of finished product molybdenum powder as seen from Figure 5, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 5.0 μm, and apparent density is 1.2g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.91%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
Embodiment 6
The method that the present embodiment utilizes ammonium molybdate to prepare molybdenum powder comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder; In the present embodiment, described ball mill is ASM type Horizontal stirring ball mill, and the ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum mass percentage is 99.98%, and diameter is the molybdenum ball of 12mm; The Fisher particle size of described ammonium molybdate powder is 6.0 μm, and the apparent density of described ammonium molybdate powder is 1.4g/cm
3; In described ammonium molybdate powder, the mass percentage of molybdenum is 54.0%; The moisture content (moisture content of ammonium molybdate powder refers to the mass percentage of water in ammonium molybdate powder) of described ammonium molybdate powder is 3.0%;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; In the present embodiment, a described reduction furnace is rotary pipe type reduction furnace, a described hydrogen reducing process adopts five warm area reduction systems, detailed process is: first all heated by five of rotary pipe type reduction furnace warm areas, make each warm area temperature be respectively 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C, then in rotary pipe type reduction furnace, pass into dew point be the hydrogen of-70 DEG C and regulate the flow velocity of hydrogen to be 10m/s; Then ammonium molybdate powder is at the uniform velocity passed through rotary pipe type reduction furnace, ammonium molybdate powder is 5h by the time that rotary pipe type reduction furnace is used, and the airflow direction of hydrogen is contrary with the traffic direction of ammonium molybdate powder; The rotary pipe type reduction furnace that described rotary pipe type reduction furnace can adopt HARPER company of the U.S. to produce;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; In the present embodiment, described secondary reduction stove is pusher 18 pipe furnaces, described secondary hydrogen reduction treatment adopts six warm area reduction systems, detailed process is: first all heated by six warm areas of pusher 18 pipe furnaces, make each warm area temperature be respectively 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C and 980 DEG C, then in pusher 18 pipe furnaces, pass into dew point be the hydrogen of-75 DEG C and regulate the flow velocity of hydrogen to be 20m/s; Then molybdenum dioxide is at the uniform velocity passed through pusher 18 pipe furnaces, molybdenum dioxide is 7.5h by the time that pusher 18 pipe furnaces are used, and the airflow direction of hydrogen is contrary with the traffic direction of molybdenum dioxide; Push type 18 pipe furnace that described pusher 18 pipe furnaces can adopt German ELINO company to produce;
Step 4, molybdenum powder rough described in step 3 is crossed 160 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; As shown in Figure 6, the epigranular of finished product molybdenum powder as seen from Figure 6, solid colour, good dispersion, reunites few the microscopic appearance of described finished product molybdenum powder, and without macroscopic mechanical admixture.
The Fisher particle size of molybdenum powder prepared by the present embodiment is 4.2 μm, and apparent density is 1.1g/cm
3; In molybdenum powder, the mass percentage of molybdenum is 99.90%; Molybdenum powder epigranular prepared by the present embodiment, chemical composition can meet the associated specifications of standard GB/T/T3461-2006, can be widely used in the raw material of the molybdenums such as molybdenum plate blank, molybdenum rod blank, molybdenum plug, molybdenum profiled piece and molybdenum alloy goods.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (6)
1. utilize ammonium molybdate to prepare a method for molybdenum powder, it is characterized in that, the method comprises the following steps:
Step one, ammonium molybdate is crossed 40 mesh sieves get oversize, then the oversize after sieving is dropped into ball milling in ball mill, obtain ammonium molybdate powder;
Step 2, in a hydrogen atmosphere, adopt a reduction furnace to carry out a hydrogen reducing process to ammonium molybdate powder described in step one, obtain molybdenum dioxide; The time of a described hydrogen reducing process is 5h ~ 6h, and the flow velocity of described hydrogen is 10m/s ~ 15m/s, and the dew point of described hydrogen is-70 DEG C ~-60 DEG C; A described hydrogen reducing process adopts four-temperature region or five warm areas reduction system, when adopting four-temperature region reduction system, the temperature of each warm area is followed successively by: 500 DEG C, 535 DEG C, 570 DEG C and 600 DEG C, and when employing five warm area reduction system, the temperature of each warm area is followed successively by 500 DEG C, 525 DEG C, 550 DEG C, 575 DEG C and 600 DEG C;
Step 3, in a hydrogen atmosphere, adopts secondary reduction stove to carry out secondary hydrogen reduction treatment to molybdenum dioxide described in step 2, obtains rough molybdenum powder; The time of described secondary hydrogen reduction treatment is 6.5h ~ 7.5h, and the flow velocity of described hydrogen is 20m/s ~ 30m/s, and the dew point of described hydrogen is-75 DEG C ~-65 DEG C; Described secondary hydrogen reduction treatment adopts three-temperature-zone, five warm areas or six warm areas reduction system, when adopting three-temperature-zone reduction system, the temperature of each warm area is followed successively by 880 DEG C, 930 DEG C and 980 DEG C, when employing five warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 905 DEG C, 930 DEG C, 955 DEG C and 980 DEG C, and when employing six warm area reduction system, the temperature of each warm area is followed successively by 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C and 980 DEG C;
Step 4, molybdenum powder rough described in step 3 is crossed 160 order ~ 200 mesh sieve extracting screen underflows, then the screenings after sieving is placed in batch mixer and mixes, obtain finished product molybdenum powder; In described finished product molybdenum powder, the mass percentage of molybdenum is not less than 99.9%.
2. a kind of method utilizing ammonium molybdate to prepare molybdenum powder according to claim 1, it is characterized in that, in ammonium molybdate powder described in step one, the mass percentage of molybdenum is not less than 54%; The moisture content of described ammonium molybdate powder is 3% ~ 5%.
3. a kind of method utilizing ammonium molybdate to prepare molybdenum powder according to claim 1, is characterized in that, the Fisher particle size of ammonium molybdate powder described in step one is 6.0 μm ~ 22.0 μm, and the apparent density of described ammonium molybdate powder is 1.0g/cm
3~ 1.5g/cm
3.
4. a kind of method utilizing ammonium molybdate to prepare molybdenum powder according to claim 1, it is characterized in that, ball mill described in step one is ASM type Horizontal stirring ball mill, ball-milling medium in described ASM type Horizontal stirring ball mill is molybdenum ball, in described molybdenum ball, the mass percentage of molybdenum is not less than 99.95%, and the diameter of described molybdenum ball is 8mm ~ 12mm.
5. a kind of method utilizing ammonium molybdate to prepare molybdenum powder according to claim 1, it is characterized in that, described in step 2, a reduction furnace is rotary pipe type reduction furnace; The stove of secondary reduction described in step 3 is pusher 18 pipe furnaces.
6. a kind of method utilizing ammonium molybdate to prepare molybdenum powder according to claim 1, is characterized in that, the Fisher particle size of finished product molybdenum powder described in step 4 is 2.0 μm ~ 5.0 μm, and the apparent density of described finished product molybdenum powder is 0.8g/cm
3~ 1.2g/cm
3.
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| CN104070176A (en) * | 2014-07-11 | 2014-10-01 | 青岛裕华电子科技有限公司 | Production method for preparing superfine molybdenum powder in low temperature reduction mode |
| CN104493191B (en) * | 2014-12-12 | 2017-02-22 | 辽宁天桥新材料科技股份有限公司 | Method for preparing large-granularity molybdenum powder with ammonium molybdate as material |
| CN105499594B (en) * | 2016-01-12 | 2018-03-30 | 金堆城钼业股份有限公司 | A kind of preparation method of micro-nano molybdenum powder |
| CN109518053B (en) * | 2018-11-30 | 2019-09-24 | 江苏东浦钨钼制品有限责任公司 | A kind of high-purity molybdenum-rhenium lanthanum ternary alloy three-partalloy guide rod and its production technology |
| CN110919020B (en) * | 2019-12-10 | 2022-10-11 | 河南科技大学 | Preparation method of molybdenum powder with large particle size |
| CN114515835B (en) * | 2022-02-25 | 2024-04-09 | 金堆城钼业光明（山东）股份有限公司 | Molybdenum powder and preparation method thereof |
| CN115323212B (en) * | 2022-09-23 | 2023-02-03 | 西安稀有金属材料研究院有限公司 | Preparation method of ultrafine molybdenum powder and molybdenum alloy with oxide nanoparticles distributed in crystal |
| CN115255379B (en) * | 2022-09-23 | 2022-12-23 | 西安稀有金属材料研究院有限公司 | Method for preparing high-dispersion ultrafine molybdenum dioxide and molybdenum powder based on chemical vapor deposition |
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