CN1594107A - Method and apparatus for preparing blue tungsten oxide by ammonium paratungstate self-reduction - Google Patents
Method and apparatus for preparing blue tungsten oxide by ammonium paratungstate self-reduction Download PDFInfo
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- CN1594107A CN1594107A CN 03139229 CN03139229A CN1594107A CN 1594107 A CN1594107 A CN 1594107A CN 03139229 CN03139229 CN 03139229 CN 03139229 A CN03139229 A CN 03139229A CN 1594107 A CN1594107 A CN 1594107A
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Abstract
The invention discloses a method and apparatus for preparing blue tungsten oxide by ammonium paratungstate self-reduction, wherein the discharging end of the preparing apparatus is provided with sealed discharger, a cooling device, an air exhaust fan and an air vent, the preparation comprises loading the ammonia paratungstate into the furnace tube of the preparing apparatus, heating the furnace tube, so as to decompose the ammonia paratungstate into WO3, ammonia gas NH3 and water vapor H2O, further decomposing the NH3 into nitrogen N2 and hydrogen H2, controlling the reaction temperature and combustion gas pressure so as to deacidize the tungsten trioxide WO3 into blue tungsten oxide.
Description
Technical Field
The invention belongs to the metal smelting technology, and particularly relates to a method and a device for preparing blue tungsten oxide by ammonium paratungstate self-reduction.
Background
The blue tungsten oxide can be used for manufacturing tungsten powder, the tungsten is the most refractory metal, the melting point is as high as about 3410 ℃, the tungsten powder is high in hardness and high in ductility and cannot be corroded by air at normal temperature, the tungsten powder is wide in application range due to the characteristics of the tungsten, for example, the tungsten powder can be used for manufacturing high-specific gravity alloys applied to automatic watch pendulums, telecommunication vibrators, airplane balance plates, X-ray, α -ray, gamma-ray protection plates and the like, and can also be used for manufacturing electrical alloys such as high-pressure contacts and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method and a device for preparing blue tungsten oxide by self-reduction of ammonium paratungstate, so that ammonia gas or mixed gas of nitrogen and hydrogen or hydrogen is not required to be introduced in the preparation process, and the use cost is reduced; meanwhile, harmful gases such as ammonia gas and the like discharged to the atmosphere can be eliminated, and the pollution to the atmosphere is greatly reduced.
The technical scheme adopted by the invention for solving the technical problems is as follows: a process for preparing blue tungsten oxide by self-reduction of ammonium paratungstate uses ammonium paratungstate 5 (NH)4)2O·12WO3·5H2O as raw material, and ammonium paratungstate 5 (NH) is fed into a container having good sealing property4)2O·12WO3·5H2O, heating the container to react with ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Thermal decomposition of O into tungsten trioxide WO3NH, ammonia gas3And water vapor H2O, the chemical reaction formula is as follows:
in the container, the tungsten oxide WO is fully utilizedXIs ammonia NH3Good catalytic properties of decomposition, NH of ammonia gas obtained by the thermal decomposition3Further decomposing into nitrogen N2And hydrogen H2The chemical reaction formula is as follows:
by controlling a certain reaction temperature and proper furnace gas pressure, hydrogen H is utilized in a container2Tungsten trioxide WO3Reduction to blue tungsten oxide WO2.9The chemical reaction formula is as follows:
at the discharge port to blue tungsten oxide WO2.9Cooling to obtain blue tungsten oxide WO2.9And (3) granules.
The ammonium paratungstate 5 (NH)4)2O·12WO3·5H2The heating temperature of O is 400-600 ℃.
The reaction temperature is controlled to be 550-800 ℃.
The pressure of the furnace gas is set to be 0-2 mbar.
The device for preparing blue tungsten oxide by ammonium paratungstate self-reduction comprises a furnace tube for reaction, wherein the furnace tube can be rotatably and obliquely arranged in a heating furnace, one end of the furnace tube is arranged as a feeding hole, the other end of the furnace tube is arranged as a discharging hole, the feeding hole is slightly higher than the discharging hole, the end part of the discharging hole is connected with a discharging hopper, the lower part of the discharging hopper is connected with a sealed discharging and cooling device, the upper part of the discharging hopper is connected with an air exhaust fan, an adjusting air valve is connected between the fan and the discharging hopper, and an air valve is connected.
The sealed discharging and cooling device comprises a screw rod used for pushing materials, a motor capable of enabling the screw rod to rotate, and a discharging pipe capable of being sleeved into the screw rod, wherein one end of the discharging pipe is fixedly connected with the bottom of the discharging hopper, a layer of water cavity used for cooling is coated outside the discharging pipe, and the feeding end part of the discharging pipe is fixedly connected with an outlet of the discharging hopper.
The feeding end of the discharge pipe is lower than the discharge end of the discharge pipe.
The screw thread arranged on the pushing screw rod is arranged at a certain distance from the outlet of the discharging hopper.
And a settling tank is also arranged between the regulating air valve and the discharge hopper.
During preparation, ammonium paratungstate 5 (NH) is put into a feed hopper at a feed inlet4)2O·12WO3·5H2O feedstock, ammonium paratungstate 5 (NH)4)2O·12WO3·5H2O is along the back taper of feeder hopperThe body slides downwards to enter the feeding pipe, and ammonium paratungstate 5 (NH) is pushed by the feeding screw in the feeding pipe4)2O·12WO3·5H2O enters the furnace tube along the feeding pipe, because the furnace tube can be rotated and obliquely arranged in the heating furnace, and the feeding hole is slightly higher than the discharging hole, under the rotation of the furnace tube, the material in the furnace can move forwards along the furnace tubeThe furnace tube is internally provided with 3-6 heating zones, each zone is provided with different heating temperatures, the feed inlet adopts a feed hopper with an inverted cone, and the discharge port is provided with a sealing discharge and cooling device, so that the furnace tube becomes a container with better sealing performance, and after the furnace tube is heated by the furnace body, ammonia paratungstate 5 (NH) enters the furnace tube4)2O·12WO3·5H2O is heated to decompose into tungsten trioxide WO under the heating temperature of 400-600 DEG C3NH, ammonia gas3And water vapor H2O, the chemical reaction formula is as follows:
when the furnace tube is heated, the furnace tube is driven by the motor and is driven by the chain wheel to rotate, so that the materials in the furnace tube can move forwards, and the furnace tube can be uniformly heated; from the above-mentioned ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Ammonia NH from thermal decomposition of O3In tungsten oxide WOXUnder the action of the catalyst, further decomposing into nitrogen N2And hydrogen H2The chemical reaction formula is as follows:
controlling the reaction temperature in the furnace tube and adjusting the pressure of the furnace gas, wherein the reaction temperature can be set to 550-800 ℃, the pressure of the furnace gas is adjusted to 0-2 mbar, the pressure adjustment of the furnace gas is realized by adjusting two valves, namely an adjusting air valve and an air valve, the adjusting air valve is arranged between the fan and the discharge hopper, the air valve is arranged between the fan and the adjusting air valve, and the purpose of adjusting the pressure of the furnace gas is realized after the two valves are adjusted; so that hydrogen H can be utilized2Tungsten trioxide WO3Reduction to blue tungsten oxide WO2.9The chemical reaction formula is as follows:
blue tungsten oxide WO2.9After the particles are formed, the particles enter the discharging hopper from the furnace tube and slide in and out along the inverted cone funnelThe material pipe and the water vapor H coming out of the furnace pipe simultaneously2O, Nitrogen N2Hydrogen gas H2And part of the micro powder enters the settling tank from the upper part of the discharge hopper under the action of the suction force of the fan, the micro powder is collected in the settling tank, and the water vapor H2O, Nitrogen N2Hydrogen gas H2Then the air is discharged into the atmosphere through a regulating air valve and a fan; because the threads arranged on the pushing screw rod are arranged at a certain distance from the outlet of the discharge hopper, and the feeding end part of the discharge pipe is lower than the discharging end part thereof, the blue tungsten oxide WO entering the discharge pipe2.9The particles form a stack at the outlet of the discharge hopper, namely the feed end of the discharge pipe, the outlet of the discharge hopper forms better sealing performance as a result of the stack, and after the stack is formed until the outlet of the discharge hopper is closed, the blue tungsten oxide WO at the edge of the stack2.9The particles are contacted with the screw thread of the pushing screw rod, the particles at the edge of the stack move to the outlet end of the discharge pipe along with the rotation of the screw rod, and the blue tungsten oxide WO2.9When the particles pass through the discharge pipe, the particles can be cooled by a layer of water cavity coated outside the discharge pipe, and the purpose of cooling is achieved.
The invention has the beneficial effect that the ammonium paratungstate 5 (NH) is adopted4)2O·12WO3·5H2O is used as raw material, and ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Thermal decomposition of O into tungsten trioxide WO3NH, ammonia gas3And water vapor H2O, and fully utilizes tungsten oxide WOXAs ammonia NH3Good catalytic properties of decomposition, NH of ammonia therein3Further decomposed into nitrogen N2And hydrogen H2Then controlling the reaction temperature and regulating the pressure of the furnace gas to react the tungsten trioxide WO3Reduction to blue tungsten oxide WO2.9So that ammonium paratungstate 5 (NH) is substituted4)2O·12WO3·5H2Ammonia NH formed by thermal decomposition of O3Is not discharged outwards, but is decomposed into nitrogen N2And hydrogen H2Post-evacuation (of which part of the hydrogen H2Tungsten trioxide WO3Reduction to blue tungsten oxide WO2.9) Is greatly reducedHarmful gases such as ammonia gas and the like discharged to the atmosphere are reducedThe resulting contamination; meanwhile, the introduction of ammonia gas or nitrogen and hydrogen mixed gas or hydrogen gas from a discharge port can be avoided, the self-reduction is realized, the preparation cost is greatly reduced, and the social and economic benefits are improved.
Drawings
The invention is further explained in detail with the accompanying drawings and the embodiments; however, the method and apparatus for preparing blue tungsten oxide by self-reduction of ammonium paratungstate according to the present invention are not limited to the examples.
FIG. 1 is a structural diagram of an apparatus for preparing blue tungsten oxide by self-reduction of ammonium paratungstate.
Detailed Description
First embodiment, referring to fig. 1, a method for preparing blue tungsten oxide from ammonium paratungstate according to the present invention is ammonium paratungstate 5 (NH)4)2O·12WO3·5H2O is used as raw material, and ammonium paratungstate 5 (NH) is fed into a furnace tube which is a container with good sealing property4)2O·12WO3·5H2O, heating the furnace tube to react with ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Thermal decomposition of O into tungsten trioxide WO3NH, ammonia gas3And water vapor H2O, the chemical reaction formula is as follows:
in the furnace tube, the tungsten oxide WO is fully utilizedXIs ammonia NH3Good catalytic properties of decomposition, NH of ammonia gas obtained by the thermal decomposition3Further decomposed into nitrogen N2And hydrogen H2The chemical reaction formula is as follows:
then, by controlling a certain reaction temperature and proper furnace gas pressure, hydrogen H is utilized in the furnace tube2Tungsten trioxide WO3Reduction to blue tungsten oxide WO2.9The chemical reaction formula is as follows:
at the discharge port to blue tungsten oxide WO2.9After cooling treatment, the blue oxide can be obtainedTungsten WO2.9And (3) granules.
The device for realizing the method for preparing the blue tungsten oxide by the self-reduction of the ammonium paratungstate comprises a furnace tube 11 for reaction, wherein the furnace tube 11 can be rotatably and obliquely arranged in a heating furnace 12, one end of the furnace tube 11 is provided with a feeding hole, the other end of the furnace tube is provided with a discharging hole, the feeding hole is slightly higher than the discharging hole, the end part of the feeding hole is connected with a feeding hopper 21, the end part of the discharging hole is connected with a discharging hopper 31, the feeding hopper 21 is fixedly connected with one end of a feeding tube 22, the feeding tube 22 is sleeved with a feeding screw 23, and; 3-6 heating zones are arranged in the heating furnace 12, and each zone is provided with different heating temperatures; the lower part of the discharge hopper 31 is connected with a sealed discharging and cooling device, the upper part of the discharge hopper 31 is connected with an air extraction fan 32, an adjusting air valve 33 is arranged between the fan 32 and the discharge hopper 31, and an air valve 34 is arranged between the fan 32 and the adjusting air valve 33.
The sealed discharging and cooling device comprises a screw 351 for pushing materials, a motor 352 capable of rotating the screw, a discharging pipe 353 capable of being sleeved in the screw, wherein one end of the discharging pipe 353 is fixedly connected with the bottom of the discharging hopper 31, a layer of water cavity 354 for cooling is coated outside the discharging pipe 353, and the feeding end part of the discharging pipe 353 is fixedly connected with the outlet of the discharging hopper 31; the feed end of the discharge pipe 353 is lower than the discharge end of the discharge pipe 353; the screw thread arranged on the pushing screw 351 is arranged at a certain distance from the outlet of the discharging hopper 31; a settling tank 36 is also arranged between the regulating air valve 33 and the discharge hopper 31.
During preparation, ammonium paratungstate 5 (NH) is put into a feed hopper 21 at the feed inlet4)2O·12WO3·5H2O feedstock, ammonium paratungstate 5 (NH)4)2O·12WO3·5H2The O slides down the inverted cone of the feed hopper 21 into the feed pipe 22 where it entersAmmonium paratungstate 5 (NH) is pushed by a feed screw 23 in a material pipe 224)2O·12WO3·5H2O enters the furnace tube 11 along the feeding tube 22, because the furnace tube 11 can be rotated and installed in the heating furnace 12, and the feeding hole is slightly higher than the discharging holeUnder the furnace tube 11 rotates, the material in the furnace can move forward along the furnace tube 11, 3 ~ 6 heating zones are arranged in the furnace tube 11, each zone is equipped with different heating temperature, because the feed inlet adopts the feeder hopper 21 of the back taper, the discharge gate is equipped with sealed ejection of compact and cooling device, the furnace tube 11 becomes a container that has better leakproofness, after the furnace tube 11 receives the heating of furnace body 12, the ammonium paratungstate 5 (NH) that gets into the furnace tube 114)2O·12WO3·5H2O is heated to decompose into tungsten trioxide WO under the heating temperature of 400 DEG C3NH, ammonia gas3And water vapor H2O, the chemical reaction formula is as follows:
when the furnace tube 11 is heated, the furnace tube 11 is driven by the motor and is driven by the chain wheel to rotate, so that the materials in the furnace tube 11 can move forwards, and the furnace tube 11 can be uniformly heated; from the above-mentioned ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Ammonia NH from thermal decomposition of O3In tungsten oxide WOXUnder the action of the catalyst, further decomposing into nitrogen N2And hydrogen H2The chemical reaction formula is as follows:
then, by controlling the reaction temperature in the furnace tube 11 and the properfurnace gas pressure, the reaction temperature can be set at 550 ℃, the pressure of the furnace gas is adjusted to 0.2 mbar, the pressure adjustment of the furnace gas is realized by adjusting two valves, namely an adjusting air valve 33 and an air valve 34, the adjusting air valve 33 is arranged between the fan 32 and the discharge hopper 31, the air valve 34 is arranged between the fan 32 and the adjusting air valve 33, and the purpose of adjusting the pressure of the furnace gas is realized after the two valves 33 and 34 are adjusted; so that hydrogen H can be utilized2Tungsten trioxide WO3Reduced to blueTungsten oxide WO2.9The chemical reaction formula is as follows:
blue tungsten oxide WO2.9After forming, the particles enter the discharging hopper 31 from the furnace tube 11 and follow the reverse coneThe body funnel slides into the discharge tube 353, at the same time as the water vapor H coming out of the furnace tube 112O, Nitrogen N2Hydrogen gas H2And part of the micro powder enters a settling tank 36 from the upper part of the discharge hopper 31 under the action of the suction force of the fan 32, the micro powder is collected in the settling tank 36, and the water vapor H2O, Nitrogen N2Hydrogen gas H2Is discharged into the atmosphere through the air valve 33 and the fan 32; because the threads arranged on the material pushing screw 351 are spaced from the outlet of the discharge hopper 31 by a certain distance, and the feeding end part of the discharge pipe 353 is lower than the discharging end part thereof, the blue tungsten oxide WO entering the discharge pipe 3532.9The particles form a stack at the outlet of the discharge hopper 31, that is, the feed end of the discharge pipe 353, the outlet of the discharge hopper 31 forms better sealing performance as a result of the stack, and the blue tungsten oxide WO at the edge of the stack is formed after the stack is formed until the outlet of the discharge hopper 31 is closed2.9The particles contact with the screw thread of the pushing screw 351, the particles at the edge of the stack move to the outlet end of the discharging pipe 353 along with the rotation of the screw 351, and the blue tungsten oxide WO2.9When the particles pass through the discharging pipe 353, the particles are cooled by a layer of water cavity 354 coated outside the discharging pipe 353, so that the purpose of cooling is achieved.
Second embodiment, referring to fig. 1, the method for preparing blue tungsten oxide from ammonium paratungstate according to the present invention is different from the first embodiment in that ammonium paratungstate 5 (NH)4)2O·12WO3·5H2When the O is heated, the heating temperature is set at 600 ℃; the reaction temperature in the furnace tube is set at 750 ℃; the furnace gas pressure was adjusted to 1.5 mbar.
Third embodiment, referring to fig. 1, the difference between the method for preparing blue tungsten oxide from ammonium paratungstate of the present invention and the first embodiment is that ammonium paratungstate 5 (NH)4)2O·12WO3·5H2O isWhen heating, the heating temperature is set at 500 ℃; the reaction temperature in the furnace tube is set at 650 ℃; the pressure of the furnace gas was adjusted to 0.5 mbar.
Claims (9)
1. A process for preparing blue tungsten oxide by self-reduction of ammonium paratungstate features that the ammonium paratungstate 5 (NH)4)2O·12WO3·5H2O is a raw material and is characterized inthat: it comprises the following steps:
a. reacting ammonium paratungstate 5 (NH)4)2O·12WO3·5H2Thermal decomposition of O into tungsten trioxide WO3NH, ammonia gas3And water vapor H2O；
b. Using tungsten oxide WOXIs ammonia NH3Good catalytic properties of decomposition, NH of ammonia gas obtained by the thermal decomposition3Further decomposed into nitrogen N2And hydrogen H2；
c. Tungsten trioxide WO is added by controlling the reaction temperature and the appropriate furnace gas pressure3Reduction to blue tungsten oxide WO2.9。
2. The method for preparing blue tungsten oxide by ammonia paratungstate self-reduction according to claim 1, wherein the method comprises the following steps: the heating temperature of the ammonium paratungstate is 400-600 ℃.
3. The method for preparing blue tungsten oxide by ammonia paratungstate self-reduction according to claim 1, wherein the method comprises the following steps: the reaction temperature is controlled to be 550-800 ℃.
4. The method for preparing blue tungsten oxide by ammonia paratungstate self-reduction according to claim 1, wherein the method comprises the following steps: the furnace gas pressure is 0-2 mbar.
5. The utility model provides a device of blue tungsten oxide of ammonium paratungstate self-reduction preparation, it includes a boiler tube that is used for the reaction, and the boiler tube is rotatable adorned in the heating furnace, and the feed inlet is established to the one end of boiler tube, and the other end is established to the discharge gate, has connect out the hopper at the tip of discharge gate, and the feed inlet is a little higher than the discharge gate, its characterized in that: the lower part of the discharge hopper is connected with a sealed discharging and cooling device, the upper part of the discharge hopper is connected with an air exhaust fan, an air adjusting valve is arranged between the fan and the discharge hopper, and an air valve is arranged between the fan and the air adjusting valve.
6. The device for preparing the blue tungsten oxide by the self-reduction of the ammonium paratungstate according to claim 5, wherein: the sealed discharging and cooling device comprises a screw rod used for pushing materials, a motor capable of enabling the screw rod to rotate, and a discharging pipe capable of being sleeved into the screw rod, wherein one end of the discharging pipe is fixedly connected with the bottom of the discharging hopper, a layer of water cavity used for cooling is coated outside the discharging pipe, and the feeding end part of the discharging pipe is fixedly connected with an outlet of the discharging hopper.
7. The device for preparing the blue tungsten oxide by the self-reduction of the ammonium paratungstate according to claim 6, wherein: the feeding end of the discharge pipe is lower than the discharge end of the discharge pipe.
8. The device for preparing the blue tungsten oxide by the self-reduction of the ammonium paratungstate according to claim 6, wherein: the screw thread arranged on the pushing screw rod is arranged at a certain distance from the outlet of the discharging hopper.
9. The device for preparing the blue tungsten oxide by the self-reduction of the ammonium paratungstate according to claim 5, wherein: and a settling tank is also arranged between the regulating air valve and the discharge hopper.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129782A1 (en) * | 2011-03-30 | 2012-10-04 | 厦门金鹭特种合金有限公司 | Preparation method of industrial purple nano-needle tungsten oxide |
| CN102923649A (en) * | 2012-11-05 | 2013-02-13 | 江苏和田科技材料有限公司 | Reduction hydrogen production compound furnace and device and method for ammonium paratungstate tungsten production by using same |
| CN103697679A (en) * | 2013-12-17 | 2014-04-02 | 许中华 | Solid and liquid separating, dehydrating and drying integrating machine |
| CN104843792A (en) * | 2015-03-23 | 2015-08-19 | 北京科技大学 | Method for preparing nano needle-shaped purple tungsten powder |
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
| CN105016393A (en) * | 2015-08-07 | 2015-11-04 | 江西稀有金属钨业控股集团有限公司 | System and method for preparing blue tungsten high in specific surface area |
| CN105645473A (en) * | 2016-03-16 | 2016-06-08 | 江西稀有金属钨业控股集团有限公司 | Preparation system and method for blue tungsten with fine particles |
| CN107572589A (en) * | 2017-10-27 | 2018-01-12 | 杭州电子科技大学 | A kind of preparation method of blue oxide tungsten nanowires |
| CN109987633A (en) * | 2017-12-29 | 2019-07-09 | 天津大学 | A kind of tungstic acid nano stick rich in Lacking oxygen, catalyst system and its preparation method and application |
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2003
- 2003-09-10 CN CN 03139229 patent/CN1238259C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129782A1 (en) * | 2011-03-30 | 2012-10-04 | 厦门金鹭特种合金有限公司 | Preparation method of industrial purple nano-needle tungsten oxide |
| US20140014875A1 (en) * | 2011-03-30 | 2014-01-16 | Chonghu Wu | Preparation method of industrial purple nano-needle tungsten oxide |
| KR101516900B1 (en) | 2011-03-30 | 2015-05-04 | 샤먼 골든 이그레트 스페셜 알로이 코., 엘티디. | Preparation method of industrial purple nano-needle tungsten oxide |
| CN102923649A (en) * | 2012-11-05 | 2013-02-13 | 江苏和田科技材料有限公司 | Reduction hydrogen production compound furnace and device and method for ammonium paratungstate tungsten production by using same |
| CN103697679A (en) * | 2013-12-17 | 2014-04-02 | 许中华 | Solid and liquid separating, dehydrating and drying integrating machine |
| CN104843792A (en) * | 2015-03-23 | 2015-08-19 | 北京科技大学 | Method for preparing nano needle-shaped purple tungsten powder |
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
| CN105016393A (en) * | 2015-08-07 | 2015-11-04 | 江西稀有金属钨业控股集团有限公司 | System and method for preparing blue tungsten high in specific surface area |
| CN105645473A (en) * | 2016-03-16 | 2016-06-08 | 江西稀有金属钨业控股集团有限公司 | Preparation system and method for blue tungsten with fine particles |
| CN107572589A (en) * | 2017-10-27 | 2018-01-12 | 杭州电子科技大学 | A kind of preparation method of blue oxide tungsten nanowires |
| CN107572589B (en) * | 2017-10-27 | 2019-08-06 | 杭州电子科技大学 | A kind of preparation method of blue oxide tungsten nanowires |
| CN109987633A (en) * | 2017-12-29 | 2019-07-09 | 天津大学 | A kind of tungstic acid nano stick rich in Lacking oxygen, catalyst system and its preparation method and application |
| CN109987633B (en) * | 2017-12-29 | 2022-03-29 | 天津大学 | Oxygen vacancy-rich tungsten trioxide porous nanorod, catalytic system, preparation method and application thereof |
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| CN1238259C (en) | 2006-01-25 |
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