CN112479259B - Yellow tungsten oxide with high specific surface area and low residual ammonia and preparation method thereof - Google Patents
Yellow tungsten oxide with high specific surface area and low residual ammonia and preparation method thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 50
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000001354 calcination Methods 0.000 claims abstract description 21
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- -1 ammonium tungsten compound Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a high specific surface area and low specific surface areaAmmonium paratungstate is added into a calcining furnace provided with six temperature control areas, and the ammonium paratungstate is sequentially subjected to oxidation calcination, cooling and sieving in the six temperature areas to obtain tungsten oxide; the temperature of the first temperature control area is 420-650 ℃; the temperature of the second temperature control area is greater than or equal to that of the first temperature control area; the temperature of the third temperature control zone is greater than or equal to the temperature of the second temperature control zone; the temperature of the fourth temperature control zone is greater than or equal to that of the third temperature control zone; the temperature of the fifth temperature control zone is greater than or equal to the temperature of the fourth temperature control zone; the temperature of the sixth temperature control area is 690-800 ℃, and is greater than or equal to the fifth temperature control. The invention has the beneficial effect that the specific surface area of the prepared yellow tungsten oxide is more than or equal to 5m 2 The residual ammonia amount is less than or equal to 0.01 percent, the surface area is large, the production of coarse tungsten powder and the coloring of composite ceramics are facilitated, and the residual ammonia amount is reduced, so that the pressure of ammonia treatment in the powder metallurgy industry is relieved.
Description
Technical Field
The invention relates to the technical field of tungsten oxide, in particular to yellow tungsten oxide with high specific surface area and low residual ammonia and a preparation method thereof.
The term "ammonium tungsten compound" is a generic term for the ammonium salt compound of tungsten and (hetero) polyacid and the calcined product thereof.
The term APT is abbreviated as "ammonium paratungstate".
The term "aqueous ammonia feed" refers to a mixture of product water, ammonia, dust, etc. after calcination of the ammonium tungsten compound.
Background
Tungsten is a refractory nonferrous metal and an important strategic resource, and is widely applied due to its excellent properties such as high melting point, high hardness, strong ductility, wear resistance, corrosion resistance and the like.
In the process of preparing metal tungsten powder by hydrogen reduction of tungsten oxide, the properties of the tungsten oxide have great influence on the reduction process and the quality of the final tungsten powder. The specific surface area of tungsten oxide refers to the total surface area of tungsten oxide powder per unit mass, and is favorable for hydrogen permeation and water vapor escape during hydrogen reduction; when the doped tungsten filament is manufactured, the tungsten oxide is required to have large specific surface and more cracks so as to be convenient for doping. Meanwhile, the tungsten oxide with high specific surface area has high chemical activity and high reduction speed, so that the boat pushing speed can be increased, the boat loading amount (or the feeding amount of the converter) can be increased, and the production efficiency of tungsten powder can be obviously improved. A great deal of literature and production practice also show that the tungsten oxide with large specific surface area is beneficial to preparing tungsten powder and tungsten carbide powder with finer granularity. At present, the technology of tungsten powder and tungsten carbide powder is developing towards the direction of ultra-fine (nano), ultra-coarsening, ultra-purification and centralization. The tungsten oxide with large specific surface area further promotes the development of ultrafine tungsten powder and tungsten carbide powder.
The yellow tungsten oxide is a finely divided yellow crystalline powder. It is to strictly control the temperature and separate the bound water or water and ammonia during the calcination of ammonium paratungstate. The precise control of time and temperature greatly affects the physical properties of tungsten oxide. In the production process of the yellow tungsten oxide, the production conditions are contradictory to the influences of the specific surface area and the residual ammonia, and generally, the high specific surface area and the low residual ammonia are difficult to be considered at the same time, but with the improvement of the environmental protection requirement, the supervision of the pollution factor ammonia is increasingly intensified, and the residual ammonia in the tungsten oxide is increasingly required to be as low as possible.
Disclosure of Invention
The invention aims to solve at least one technical problem in the prior art and provides yellow tungsten oxide with high specific surface area and low residual ammonia and a preparation method thereof.
The technical solution of the invention is as follows:
a preparation method of yellow tungsten oxide with high specific surface area and low residual ammonia comprises the following steps: adding a raw material ammonium paratungstate into a calcining furnace provided with six temperature control areas, sequentially carrying out oxidation calcination, cooling and sieving on the ammonium paratungstate in the six temperature control areas to obtain tungsten oxide; wherein,
the temperature of the first temperature control area is 420-650 ℃;
the temperature of the second temperature control area is greater than or equal to that of the first temperature control area;
the temperature of the third temperature control zone is greater than or equal to the temperature of the second temperature control zone;
the temperature of the fourth temperature control zone is greater than or equal to the temperature of the third temperature control zone;
the temperature of the fifth temperature control zone is greater than or equal to the temperature of the fourth temperature control zone;
the temperature of the sixth temperature control area is more than or equal to that of the fifth temperature control area, and the temperature of the sixth temperature control area is 690-800 ℃.
Preferably, the temperature difference between the second temperature control region and the first temperature control region is 0-50 ℃, the temperature difference between the third temperature control region and the second temperature control region is 0-50 ℃, the temperature difference between the fourth temperature control region and the third temperature control region is 0-50 ℃, the temperature difference between the fifth temperature control region and the fourth temperature control region is 0-150 ℃, and the temperature difference between the sixth temperature control region and the fifth temperature control region is 0-50 ℃.
Preferably, the temperature of the second temperature control area is 450-680 ℃; the temperature of the third temperature control area is 550-700 ℃; the temperature of the fourth temperature control area is 600-700 ℃; the temperature of the fifth temperature control area is 650-800 ℃.
Preferably, the temperature of the first temperature control area is 450-650 ℃; the temperature of the second temperature control area is 450-660 ℃; the temperature of the third temperature control area is 600-670 ℃; the temperature of the fourth temperature control area is 600-680 ℃; the temperature of the fifth temperature control area is 690-750 ℃; the temperature of the sixth temperature control area is 690-750 ℃.
Preferably, the temperature of the first temperature control zone is 650 ℃; the temperature of the second temperature control area is 660 ℃; the temperature of the third temperature control area is 670 ℃; the temperature of the fourth temperature control area is 680 ℃; the temperature of the fifth temperature control area is 690 ℃; the temperature of the sixth temperature control zone was 690 ℃.
Preferably, the temperature of the first temperature control zone is 550 ℃; the temperature of the second temperature control area is 600 ℃; the temperature of the third temperature control area is 600 ℃; the temperature of the fourth temperature control area is 600 ℃; the temperature of the fifth temperature control area is 720 ℃; the temperature of the sixth temperature control zone was 720 ℃.
Preferably, the temperature of the first temperature control zone is 450 ℃; the temperature of the second temperature control zone is 450 ℃; the temperature of the third temperature control area is 600 ℃; the temperature of the fourth temperature control area is 600 ℃; the temperature of the fifth temperature control area is 750 ℃; the temperature of the sixth temperature control zone was 750 ℃.
Preferably, the relative vacuum degree in the furnace chamber is-40 Pa to-200 Pa.
Preferably, the rotating speed of the furnace tube is 1.5-2.5r/min.
The yellow tungsten oxide with high specific surface area and low residual ammonia is prepared by the preparation method of the yellow tungsten oxide with high specific surface area and low residual ammonia, and the specific surface area is more than or equal to 5m 2 The residual ammonia amount is less than or equal to 0.01 percent per gram.
The invention has at least one of the following beneficial effects:
the method ensures that the prepared yellow tungsten oxide has the characteristics of high specific surface area and low residual ammonia by controlling the heating temperature of six temperature control areas in the calcination, the vacuum degree in the hearth and the rotating speed of the furnace tube, and the specific surface area of the yellow tungsten oxide is more than or equal to 5m 2 The residual ammonia amount is less than or equal to 0.01 percent, has the advantages of large chemical activity and large adsorption capacity, is beneficial to producing coarse tungsten powder and coloring composite ceramics, and simultaneously reduces the residual ammonia amount, thereby relieving the pressure of ammonia treatment in the powder metallurgy industry.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
A preparation method of yellow tungsten oxide with high specific surface area and low residual ammonia comprises the steps of adding a raw material ammonium tungsten compound into a calcining furnace provided with six temperature control areas, sequentially carrying out oxidation and calcination on ammonium paratungstate in the six temperature control areas, and ensuring that the relative vacuum degree in a hearth is-40 to-200 Pa; the rotating speed of the furnace tube is 1.5-2.5r/min; the calcination time is 30-60 min, after the calcination is finished, the product is cooled and sieved to obtain the product with the specific surface area more than or equal to 5m 2 Tungsten oxide with residual ammonia content less than or equal to 0.01 percent;
wherein the temperature of the first temperature control area is 420-650 ℃; the temperature of the second temperature control area is more than or equal to that of the first temperature control area, and the temperature difference is 0-50 ℃; the temperature of the third temperature control area is greater than or equal to that of the second temperature control area, and the temperature difference is 0-50 ℃; the temperature of the fourth temperature control area is more than or equal to that of the third temperature control area, and the temperature difference is 0-50 ℃; the temperature of the fifth temperature control area is more than or equal to that of the fourth temperature control area, and the temperature difference is 0-150 ℃; the temperature of the sixth temperature control area is greater than or equal to that of the fifth temperature control area, the temperature difference is 0-50 ℃, and the temperature of the sixth temperature control area is 690-800 ℃.
Preferably, the temperature of the second temperature control area is 450-680 ℃; the temperature of the third temperature control area is 550-700 ℃; the temperature of the fourth temperature control area is 600-700 ℃; the temperature of the fifth temperature control area is 650-800 ℃.
More preferably, the temperature of the first temperature control zone is 450-650 ℃; the temperature of the second temperature control area is 450-660 ℃; the temperature of the third temperature control area is 600-670 ℃; the temperature of the fourth temperature control area is 600-680 ℃; the temperature of the fifth temperature control area is 690-750 ℃; the temperature of the sixth temperature control area is 690-750 ℃.
Wherein, the calcining furnace is a rotary furnace.
The ammonium tungsten compound is preferably ammonium paratungstate.
Example 1
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-40 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control zone is 650 ℃, the second temperature control zone is 660 ℃, the third temperature control zone is 670 ℃, the fourth temperature control zone is 680 ℃, the fifth temperature control zone is 690 ℃, the sixth temperature control zone is 690 ℃, the rotating speed of the furnace tube is 1.5r/min, the obtained product is calcined by a rotary furnace, cooled and sieved, and the specific surface area is more than or equal to 5m 2 Yellow tungsten oxide with residual ammonia content less than or equal to 0.01 percent.
Example 2
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-100 Pa by a screw feeder at the speed of 180kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control zone is 550 ℃ atThe second temperature control zone is 600 ℃, the third temperature control zone is 600 ℃, the fourth temperature control zone is 600 ℃, the fifth temperature control zone is 720 ℃, the sixth temperature control zone is 720 ℃, the furnace tube rotating speed is 1.8r/min, the obtained product is calcined by a rotary furnace, cooled and sieved, and the prepared specific surface area is not less than 5m 2 Yellow tungsten oxide with the residual ammonia content of less than or equal to 0.01 percent.
Example 3
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-150 Pa by a screw feeder at the speed of 150kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature to be as follows: the first temperature control area is 450 ℃, the second temperature control area is 450 ℃, the third temperature control area is 600 ℃, the fourth temperature control area is 600 ℃, the fifth temperature control area is 750 ℃, the sixth temperature control area is 750 ℃, the rotating speed of the furnace tube is 2.2r/min, the obtained product is cooled and sieved after being calcined by a rotary furnace, and the prepared specific surface area is more than or equal to 5m 2 Yellow tungsten oxide with residual ammonia content less than or equal to 0.01 percent.
Example 4
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-200 Pa by a screw feeder at the speed of 180kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature to be as follows: the first temperature control area is 600 ℃, the second temperature control area is 620 ℃, the third temperature control area is 650 ℃, the fourth temperature control area is 680 ℃, the fifth temperature control area is 750 ℃, the sixth temperature control area is 800 ℃, the rotating speed of the furnace tube is 2.5r/min, the mixture is calcined by a rotary furnace, cooled and sieved, and the specific surface area is more than or equal to 5m 2 Yellow tungsten oxide with residual ammonia content less than or equal to 0.01 percent.
Example 5
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-80 Pa by a screw feeder at the speed of 150kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control zone is 420 ℃, the second temperature control zone is 450 ℃, the third temperature control zone is 500 ℃, the fourth temperature control zone is 580 ℃, the fifth temperature control zone is 730 ℃, the sixth temperature control zone is 760 ℃, the rotating speed of a furnace tube is 2.0r/min, the mixture is calcined by a rotary furnace, cooled and sieved to obtain the product with the specific surface area of more than or equal to 5m 2 Yellow tungsten oxide with the residual ammonia content of less than or equal to 0.01 percent.
Example 6
Putting APT into a feeding bin, feeding the APT into a rotary furnace with relative vacuum degree of-180 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control area is 500 ℃, the second temperature control area is 500 ℃, the third temperature control area is 550 ℃, the fourth temperature control area is 590 ℃, the fifth temperature control area is 700 ℃, the sixth temperature control area is 750 ℃, the rotating speed of the furnace tube is 2.2r/min, the mixture is calcined by a rotary furnace, cooled and sieved, and the specific surface area is more than or equal to 5m 2 Yellow tungsten oxide with residual ammonia content less than or equal to 0.01 percent.
Comparative example 1
Putting APT into a feeding bin, feeding into a rotary furnace with the relative vacuum degree of-40 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature to be as follows: the first temperature control area is 300 ℃, the second temperature control area is 300 ℃, the third temperature control area is 650 ℃, the fourth temperature control area is 650 ℃, the fifth temperature control area is 700 ℃, the sixth temperature control area is 750 ℃, the rotating speed of the furnace tube is 1.0r/min, and the yellow tungsten oxide is prepared by cooling and sieving after the calcination of the rotary furnace.
Comparative example 2
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-40 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control area is 400 ℃, the second temperature control area is 400 ℃, the third temperature control area is 700 ℃, the fourth temperature control area is 800 ℃, the fifth temperature control area is 800 ℃, the sixth temperature control area is 800 ℃, the rotating speed of the furnace tube is 3.0r/min, and the yellow tungsten oxide is prepared after the materials are calcined by the rotary furnace, cooled and sieved.
Comparative example 3
Putting APT into a feeding bin, feeding the APT into a rotary furnace with the relative vacuum degree of-300 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature as follows: the first temperature control area is 350 ℃, the second temperature control area is 350 ℃, the third temperature control area is 700 ℃, the fourth temperature control area is 750 ℃, the fifth temperature control area is 800 ℃, the sixth temperature control area is 800 ℃, the rotating speed of the furnace tube is 1.5r/min, and the yellow tungsten oxide is prepared after the materials are calcined by the rotary furnace, cooled and sieved.
Comparative example 4
Putting APT into a feeding bin, feeding into a rotary furnace with the relative vacuum degree of-10 Pa by a screw feeder at the speed of 200kg/h, opening a furnace tail observation mirror to form an open system, and controlling the temperature to be as follows: the first temperature control area is 420 ℃, the second temperature control area is 450 ℃, the third temperature control area is 500 ℃, the fourth temperature control area is 750 ℃, the fifth temperature control area is 850 ℃ and the sixth temperature control area is 800 ℃, the rotating speed of a furnace tube is 1.5r/min, and the yellow tungsten oxide is prepared by cooling and sieving after the calcination of a rotary furnace.
The specific surface area and the residual ammonia amount of the yellow tungsten oxide prepared in the examples 1 to 6 and the comparative examples 1 to 4 were measured, wherein the specific surface area was measured according to the method in the national standard GB119587, and the residual ammonia amount was measured according to the method in the national standard GB/T4324.26-2012, and the measurement results are shown in table 1:
TABLE 1
| Item | Specific surface area (m) 2 /g) | Residual ammonia (%) |
| Example 1 | 5.2 | 0.0098 |
| Example 2 | 6.2 | 0.0080 |
| Example 3 | 7.8 | 0.0050 |
| Example 4 | 7.5 | 0.0044 |
| Example 5 | 6.5 | 0.0051 |
| Example 6 | 5.4 | 0.0062 |
| Comparative example 1 | 2.991 | 0.011 |
| Comparative example 2 | 3.554 | 0.006 |
| Comparative example 3 | 1.027 | 0.003 |
| Comparative example 4 | 1.478 | 0.007 |
As can be seen from Table 1, the specific surface areas of the yellow tungsten oxides obtained in examples 1 to 6 were each larger than 5m 2 G, maximum 7.8m 2 The residual ammonia amount is less than 0.01 percent and the minimum is 0.0044 percent. As can be seen from comparison of examples 1 to 6 with comparative examples 1 to 4, the specific surface areas of the yellow tungsten oxides obtained in examples 1 to 6 are all larger than those of comparative examplesExample 1 (calcination temperature and furnace tube rotation speed are different from those of the examples), comparative example 2 (calcination temperature and furnace tube rotation speed are different from those of the examples), comparative example 3 (calcination temperature and vacuum degree are different from those of the examples), and comparative example 4 (calcination temperature and vacuum degree are different from those of the examples), from which it can be seen that the calcination temperature, furnace tube rotation speed, and vacuum degree in the calciner significantly affect the specific surface area and residual ammonia amount of the yellow tungsten oxide.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by adopting the equivalent exchange or the equivalent substitution fall within the protection scope of the present invention.
Claims (7)
1. A preparation method of yellow tungsten oxide with high specific surface area and low residual ammonia is characterized by comprising the following steps: adding a raw material ammonium paratungstate into a rotary furnace provided with six temperature control areas, sequentially carrying out oxidation calcination, cooling and sieving on the ammonium paratungstate in the six temperature control areas to obtain tungsten oxide; wherein,
the temperature of the first temperature control area is 420 to 650 ℃;
the temperature of the second temperature control area is greater than or equal to that of the first temperature control area;
the temperature of the third temperature control zone is greater than or equal to the temperature of the second temperature control zone;
the temperature of the fourth temperature control zone is greater than or equal to the temperature of the third temperature control zone;
the temperature of the fifth temperature control zone is greater than or equal to the temperature of the fourth temperature control zone;
the temperature of the sixth temperature control area is 690-800 ℃, and is more than or equal to the fifth temperature control area;
the temperature difference between the second temperature control area and the first temperature control area ranges from 0 ℃ to 50 ℃, the temperature difference between the third temperature control area and the second temperature control area ranges from 0 ℃ to 50 ℃, the temperature difference between the fourth temperature control area and the third temperature control area ranges from 0 ℃ to 50 ℃, the temperature difference between the fifth temperature control area and the fourth temperature control area ranges from 0 ℃ to 150 ℃, and the temperature difference between the sixth temperature control area and the fifth temperature control area ranges from 0 ℃ to 50 ℃;
the relative vacuum degree in the hearth ranges from minus 40Pa to minus 200Pa; the rotating speed of the furnace tube is 1.5-2.5r/min; the calcination time is 30 to 60min.
2. The preparation method of the yellow tungsten oxide with high specific surface area and low residual ammonia according to claim 1, wherein the temperature of the second temperature control area is 450-680 ℃; the temperature of the third temperature control area is 550 to 700 ℃; the temperature of a fourth temperature control area is 600 to 700 ℃; the temperature of the fifth temperature control zone is 650 to 800 ℃.
3. The preparation method of the yellow tungsten oxide with high specific surface area and low residual ammonia according to claim 1, wherein the temperature of the first temperature control area is 450-650 ℃; the temperature of the second temperature control area is 450 to 660 ℃; the temperature of the third temperature control area is 600 to 670 ℃; the temperature of a fourth temperature control area is 600 to 680 ℃; the temperature of the fifth temperature control area is 690 to 750 ℃; the temperature in the sixth temperature control zone is 690 to 750 ℃.
4. The method for preparing yellow tungsten oxide with high specific surface area and low residual ammonia according to claim 1, wherein the temperature of the first temperature control area is 650 ℃; the temperature of the second temperature control area is 660 ℃; the temperature of the third temperature control area is 670 ℃; the temperature of the fourth temperature control area is 680 ℃; the temperature of the fifth temperature control area is 690 ℃; the temperature of the sixth temperature control zone was 690 ℃.
5. The method for preparing the yellow tungsten oxide with high specific surface area and low residual ammonia according to claim 1, wherein the temperature of the first temperature control area is 550 ℃; the temperature of the second temperature control area is 600 ℃; the temperature of the third temperature control area is 600 ℃; the temperature of the fourth temperature control area is 600 ℃; the temperature of the fifth temperature control area is 720 ℃; the temperature of the sixth temperature control zone was 720 ℃.
6. The method for preparing yellow tungsten oxide with high specific surface area and low residual ammonia according to claim 1, wherein the temperature of the first temperature control area is 450 ℃; the temperature of the second temperature control zone is 450 ℃; the temperature of the third temperature control area is 600 ℃; the temperature of the fourth temperature control area is 600 ℃; the temperature of the fifth temperature control area is 750 ℃; the temperature in the sixth temperature control zone was 750 ℃.
7. The yellow tungsten oxide with high specific surface area and low residual ammonia is characterized by being prepared by the preparation method of the yellow tungsten oxide with high specific surface area and low residual ammonia according to claims 1-6, wherein the specific surface area is more than or equal to 5m 2 The residual ammonia amount is less than or equal to 0.01 percent per gram.
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