CN102942222A - Method for preparing ammonium tungstate by treating waste tungsten oxide - Google Patents
Method for preparing ammonium tungstate by treating waste tungsten oxide Download PDFInfo
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- CN102942222A CN102942222A CN201210442550XA CN201210442550A CN102942222A CN 102942222 A CN102942222 A CN 102942222A CN 201210442550X A CN201210442550X A CN 201210442550XA CN 201210442550 A CN201210442550 A CN 201210442550A CN 102942222 A CN102942222 A CN 102942222A
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Abstract
The invention discloses a method for preparing ammonium tungstate by treating waste tungsten oxide, which comprises the following steps of: adopting an ammonia water pressure cooking method to dissolve waste tungsten trioxide, blue tungsten oxide, and other tungsten oxide to prepare an ammonium tungstate solution, ammonium paratungstate, ammonium metatungstate and other ammonium tungstate. Compared the method that caustic soda or soda ash digestion or melting-poaching is adopted to dissolve the tungsten oxide to prepare a sodium tungstate solution, and the method that a solvent extraction or ion exchange process is adopted to prepare the sodium tungstate solution in the prior art, the method has the advantages and characteristics that the procedure process can be simplified, the auxiliary raw materials can be saved, energy saving and emission reduction can be realized, the environmental pollution can be relieved, and the production cost can be reduced.
Description
Technical field
The present invention relates to a kind of method that waste and old Tungsten oxide 99.999 is produced ammonium tungstate that recycles, the said waste and old Tungsten oxide 99.999 of the present invention comprises written-off, quality does not reach service requirements and must do over again and improve the tungstic oxide of quality index, the Tungsten oxide 99.999s such as blue tungsten oxide, said ammonium tungstate comprises ammonium tungstate solution, ammonium paratungstate (English name abbreviation APT), ammonium metawolframate (English name abbreviation AMT) etc., specifically, relate to a kind of the pressure with ammoniacal liquor and boil the waste and old tungstic oxide of dissolving, the mixture of blue tungsten oxide and multiple Tungsten oxide 99.999, make ammonium tungstate solution, and from the ammonium tungstate solution that obtains with this method, produce ammonium paratungstate, the tungsten smelting process of the ammonium tungstates such as ammonium metawolframate.
Background technology
According to " tungsten smelting principle and technique " (not like great work, light industry press publishes), " tungsten is metallurgical " (Zhang Qixiu, the Zhao Qinsheng work, metallurgical industry press), " tungsten is metallurgical " (Wan Linsheng work), the tungsten such as " Chinese Tungsten Industry " (Chinese Tungsten Industry association sponsors) are smelted authoritative monograph and are smelted relevant patented technology with the authoritative magazine of national tungsten industry and retrieval with tungsten, the waste and old Tungsten oxide 99.999 of domestic and international existing recycling is produced ammonium tungstate solution at present, ammonium paratungstate, the processing method of ammonium metawolframate, all tungstic oxide and blue tungsten oxide are all insoluble or be slightly soluble in ammoniacal liquor before all being based on, only be dissolved in the chemical property of caustic soda or soda ash, all be to use in advance caustic soda (sodium hydroxide) solution or soda ash (yellow soda ash) solution normal pressure or pressure to boil dissolved oxygen tungsten on the technique, make sodium tungstate solution, or with soda ash (yellow soda ash) high-temperature fusion Tungsten oxide 99.999, then leach tungsten through poach, make sodium tungstate solution.Subsequent technique can divide three classes: the first kind is by organic solvent extraction tungsten and ammoniacal liquor reextraction tungsten with sodium tungstate solution, make ammonium tungstate solution, at last with the evaporative crystallization method or or in and crystallization process from ammonium tungstate solution, produce the tungstate such as ammonium paratungstate, ammonium metawolframate.Equations of The Second Kind be with sodium tungstate solution by ion exchange resin absorption tungsten and ammoniacal liquor desorb tungsten, make tungsten change into ammonium tungstate solution, at last with the evaporative crystallization method or in from ammonium tungstate solution, produce the tungstate such as ammonium paratungstate, ammonium metawolframate with crystallization process.The 3rd class is that sodium tungstate solution is precipitated artificial scheelite (calcium wolframate) with calcium chloride, decompose artificial scheelite with hydrochloric acid again and make wolframic acid, then use the ammonia solvent wolframic acid, make ammonium tungstate solution, at last with the evaporative crystallization method or in and crystallization process from ammonium tungstate solution, produce the tungstate such as ammonium paratungstate, ammonium metawolframate.
Although above-mentioned prior art can reach purpose and the technical requirements of tungstate such as producing ammonium tungstate solution, ammonium paratungstate, ammonium metawolframate, also has following shortcoming: (1) consumes caustic soda, soda ash and the hydrochloric acid of great quantities of spare; (2) technical process and production time are longer; (3) facility investment is larger; (4) production cost is higher, the market competitive power that causes product a little less than.
Goal of the invention
The objective of the invention is to overcome defects, provide a kind of than prior art more simplification of flowsheet, the preparation method who produces the ammonium tungstates such as ammonium tungstate solution, ammonium paratungstate, ammonium metawolframate that saves auxiliary material and the energy, alleviate environmental pollution, reduce production costs.
Summary of the invention
Test finds that the Tungsten oxide 99.999s such as tungstic oxide, blue tungsten oxide are resolved into ammonium tungstate solution by the ammoniacal liquor under the high-temperature and high-pressure conditions easily, and have higher tungsten solubleness after deliberation.This is a kind of new chemical property of Tungsten oxide 99.999.The present invention is exactly the technical scheme of formulating according to this property research of Tungsten oxide 99.999.
Technical solution of the present invention is the character that is easily resolved into ammonium tungstate solution according to Tungsten oxide 99.999 by the ammoniacal liquor under the High Temperature High Pressure, boil proportion scale according to pressure provided by the invention, the ammoniacal liquor and the waste and old Tungsten oxide 99.999 material that under agitation add aequum in the autoclave, to containing the material of blue tungsten oxide, add tungsten with lower valency to be oxidized to+hydrogen peroxide (superoxol) of the theoretical reacting weight 120～150% of 6 valency tungsten, add hot pressing and boil, vapor pressure is at 0.5kg/cm in the control still
2More than, for operational safety and saving time, vapor pressure is with 4～10kg/cm in the still
2The most suitable, according to the coarse size details condition of still internal pressure and Tungsten oxide 99.999, pressing and boiling the reaction times is 10～300 minutes, for operational safety and saving time, it is the most suitable with 60～180 minutes that pressure is boiled the time, and reaction finishes, stopped heating, be cooled to normal temperature and pressure, check solution colour, as aobvious blue, add again hydrogen peroxide and disappear to blue, regulating control solution the concentration of free ammonia is 3～5%, and tungstic oxide concentration is 120～350 grams per liters in the control ammonium tungstate solution.Then adopt existing ordinary method with ammonium tungstate solution by evaporating, concentrating and crystallizing or in and crystallization produce the ammonium paratungstate that different performance and purposes require; Ammonium tungstate solution is produced ammonium metawolframate by neutralization conversion-spraying drying; Ammonium paratungstate is produced ammonium metawolframate by calcining conversion-digestion-spraying drying; Ammonium paratungstate is produced ammonium metawolframate by neutralization conversion-spraying drying.
It is as follows that pressure is boiled proportion scale:
(1) ammonia concn: strong aqua is diluted with deionized water (hereinafter to be referred as water), or water absorption liquefied ammonia is made the weak ammonia that contains ammonia 8～20%;
(2) waste and old Tungsten oxide 99.999 weight/weak ammonia volume=150～350 grams per liters.
Embodiment
Of the present inventionly a kind ofly process waste and old Tungsten oxide 99.999 to produce the method for the ammonium tungstates such as ammonium tungstate solution, ammonium paratungstate, ammonium metawolframate as follows:
One, raw material is processed
Waste and old Tungsten oxide 99.999 first by 60～80 mesh sieves, is removed Tungsten oxide 99.999 and the mechanical inclusion of caking, again the Tungsten oxide 99.999 stone roller essence of caking is also all sieved.
Two, pressure is boiled proportion scale
(1) ammonia concn: strong aqua is diluted with deionized water (hereinafter to be referred as water), or water absorption liquefied ammonia is made the weak ammonia that contains ammonia 8～20%;
(2) waste and old Tungsten oxide 99.999 weight/ammoniacal liquor volume=150～350 grams per liters.
Three, ammonia presses boiling to get ammonium tungstate solution
(1) according to the useful volume of the autoclave weight of the pending Tungsten oxide 99.999 of calculative determination in advance, again according to the required weak ammonia volume of the weight calculative determination of Tungsten oxide 99.999, or determines the weight of required Tungsten oxide 99.999 according to the weak ammonia volume calculation.
(2) under agitation add weak ammonia and the waste and old Tungsten oxide 99.999 material of aequum in the autoclave of enamel material or stainless steel, to containing the material of blue tungsten oxide, add tungsten with low state to be oxidized to+hydrogen peroxide of the theoretical reacting weight 120～150% of 6 valency tungsten, compress kettle cover, under constantly stirring, slowly be heated in the still vapor pressure at 0.5kg/cm
2More than, for operational safety and saving time, vapor pressure is with 4～10kg/cm in the still
2The most suitable, according to the granularity thickness of still internal pressure and Tungsten oxide 99.999, pressing and boiling the reaction times is 10～300 minutes, for operational safety and saving time, it is the most suitable with 60～180 minutes that pressure is boiled the reaction times, and reaction finishes, stopped heating, be cooled to normal temperature (20～40 ℃), check solution colour, as aobvious blue, add again hydrogen peroxide and disappear to blue, regulating the concentration of free ammonia with ammoniacal liquor or water is 3～5%, and tungstic oxide concentration is 120～350 grams per liters in the control ammonium tungstate solution.
(3) will be cooled to the ammonium tungstate solution of normal temperature by vacuum filtration or centrifuging or press filtration, filtrate changes the ammonium tungstate solution storage tank over to and left standstill 10～30 hours, and the purpose that leaves standstill is to make part foreign ion residual in the solution through ageing and crystallization is deposited to bottom land.
Four, ammonium paratungstate produces
(1) ammonium tungstate solution after will leaving standstill is emitted and is changed over to the evaporative crystallization reactor of enamel material or stainless steel from exceeding the outlet that staticizes more than the bottom land 20cm, be heated to and boil, the insulation evaporation concentration is separated out a large amount of white ammonium para-tungstate crystals, stopped heating when solution proportion is down to 1.08～1.05, stirring is cooled to below 90 ℃, solution is put into vacuumfilter or centrifugal filter filtration together with ammonium para-tungstate crystal, wash with water 3～4 times.
(2) ammonium para-tungstate crystal that filtration washing is good is packed in the charging basin of drying chamber of stainless steel, or in the fluidized bed type dryer, or in the rotary kiln, in 80～130 ℃ of oven dry.By 80 mesh sieves, be the finished product ammonium paratungstate through check, packing again after the cooling.
Five, ammonium metawolframate produces
1, in and the ammonium tungstate solution conversion method
(1) in and ammonium tungstate solution
Ammonium tungstate solution after leaving standstill is changed in the enamel double layer evaporation crystallization reaction still, be heated to more than 50 ℃, under agitation slowly drip 1～10% dilute nitric acid solution, be neutralized to solution-stabilized at PH 2～4, all be converted into ammonium metatungstate solution to the ammonium para-tungstate crystal of separating out, stop immediately neutralization this moment.
(2) spray-drying process is produced ammonium metawolframate
The ammonium metatungstate solution that neutralization is transformed continues to be heated to boiling, and the insulation evaporation concentration is to solution proportion 1.3～1.5, and stopped heating with the spray-dried machine spraying drying of this concentrated solution, makes ammonium metatungstate crystal while hot.
2, calcining ammonium paratungstate conversion method
(1) calcining ammonium paratungstate
Ammonium paratungstate is packed in the rotary kiln, slowly heat up, the control calcining temperature is at 150～330 ℃, and the control residing time in furnace is 20～120 minutes, makes ammonium paratungstate lose part ammonia and crystal water, and calcining material 80～100% is converted into ammonium metawolframate soluble in water.Calcining temperature is higher, and the residence time is shorter, otherwise calcining temperature is lower, then needs time of stopping longer.The pH value of at any time inspection by sampling water dissolution rate in the calcination process (or claiming leaching yield) and the aqueous solution, dissolution rate should reach more than 80%, preferably can reach 100%, and the pH value of the control aqueous solution is 2～4.When dissolution rate is lower than 70%, and pH value is higher than at 4 o'clock, need to continue to prolong calcination time qualified to dissolution rate and pH value till.
(2) poach dissolving ammonium metawolframate
Ratio in calcining material weight/volume of water=150～200 grams per liters, under agitation water and calcining material are successively added in the evaporative crystallization reactor of enamel material material or stainless steel, add the calcining material after preferably adding first water, after slurry stirs, be heated to 70～100 ℃, keep little digestion of boiling, add the moisture content of water evaporation, substantially keep original volume.The digestion time is 30～180 minutes, centre at any time inspection by sampling solution pH value is 2～4, when dissolution rate reaches maximum value, it is stopped heating, filtered while hot, filter residue hot water wash 3～4 times, filtrate is ammonium metatungstate solution, change ammonium metatungstate solution over to and leave standstill groove, leave standstill after 8～24 hours and carry out condensing crystal.The filter residue major ingredient is the Tungsten oxide 99.999 that calcining excessively generates, and returns the ammoniacal liquor pressure after the collection and boils again recovery.
(3) spray-drying process is produced ammonium metawolframate
The ammonium metatungstate solution that digestion is filtered changes in the evaporative crystallization reactor of enamel material material or stainless steel, be heated to boil and keep the boiling, evaporation concentration is to solution proportion 1.3～1.5, stopped heating, with the spray-dried machine spraying drying of this concentrated solution, make ammonium metatungstate crystal while hot.
3, in and the ammonium paratungstate conversion method
(1) in and ammonium paratungstate
The water that adds first its useful volume 40～50% in the enamel reaction still, the ammonium paratungstate that under agitation slowly adds aequum, be heated to 70～90 ℃, slowly thread adds 5～10% dilute nitric acid solution and is neutralized to and solution-stabilizedly all dissolves at PH=2～4 to ammonium paratungstate, stop neutralization, if be lower than PH=2, then slowly add the anti-PH=2 of transferring to of weak ammonia～4, if be higher than PH=4, then continue to be neutralized to PH=2～4.At this moment, ammonium paratungstate all is converted into ammonium metatungstate solution.
(2) spray-drying process is produced ammonium metawolframate
The ammonium metatungstate solution that neutralization is transformed continues to be heated to boiling, and the insulation evaporation concentration is to solution proportion 1.3～1.5, and stopped heating with the spray-dried machine spraying drying of this concentrated solution, makes ammonium metatungstate crystal while hot.
Of the present inventionly a kind ofly process method that waste and old Tungsten oxide 99.999 produces ammonium tungstate compared with prior art, have the following advantages:
(1) simplifies technical process, shortened the production cycle;
(2) save the consumption of caustic soda, soda ash and the hydrochloric acid of great quantities of spare, reduced production cost;
(3) do not use strong acid and strong base, reduced the environmental protection cost of processing a large amount of waste water and gas;
(4) save the energy, reduced the discharging of pollutent.
Embodiment
A kind ofly process waste and old Tungsten oxide 99.999 and produce the method for ammonium tungstate and be further described of the present invention below in conjunction with embodiment, but be not limitation of the invention.
One, pressure is boiled proportion scale
(1) waste and old Tungsten oxide 99.999 treatment capacity: the every autoclave of present embodiment is processed 300 kilograms of waste and old tungstic oxides, and 150 kilograms of blue tungsten oxides amount to 450 kilograms of mixed oxidization tungsten after mixing.
(2) ammonia concn: with the strong aqua dilute with water, make the weak ammonia that contains ammonia 14%.
(3) waste and old Tungsten oxide 99.999 weight/weak ammonia volume is 321 grams per liters.
Two, processing step
1, ammonia presses boiling to get ammonium tungstate solution
(1) be to add 1310 liters of weak ammonias in 2000 liters the enamel autoclave to volume under agitation, 450 kilograms in mixed oxidization tungsten, slowly add 185 liters in technical grade hydrogen peroxide, compress kettle cover, under constantly stirring, slowly be heated in the still vapor pressure at 4～6kg/cm
2, to press and boiled 110 minutes, stopped heating is cooled to 35 ℃, successively regulates the concentration of free ammonia to 3.8% with ammoniacal liquor and water, and tungstic oxide concentration is 276 grams per liters.
The ammonium tungstate solution that (2) will be cooled to normal temperature is by stainless-steel vacuum suction filter suction filtration, filtrate change over to the ammonium tungstate solution storage tank leave standstill 24 hours stand-by.
2, ammonium paratungstate produces
(1) ammonium tungstate solution after will leaving standstill is from exceeding the outlet that staticizes bottom land 20cm and emitting and to change volume over to be 2000 liters the enamel evaporative crystallization still, be heated to and boil, the insulation evaporation concentration is separated out a large amount of white ammonium para-tungstate crystals, solution proportion is down to 1.06 o'clock stopped heatings, stirring is cooled to 80 ℃, solution is put into stainless-steel vacuum suction filter suction filtration together with ammonium para-tungstate crystal, wash with water 3～4 times.
(2) during the ammonium para-tungstate crystal that filtration washing is good was packed drying chamber with stainless steel charging basin into, charging thickness was 3～5cm, in 100～130 ℃ of oven dry.By 80 mesh sieves, be the finished product ammonium paratungstate through check, packing again after the cooling.
3, ammonium metawolframate produces
(1) calcining ammonium paratungstate
Ammonium paratungstate is packed in the stainless steel rotary kiln of diameter 300mm, slowly heat up, the control calcining temperature is at 245～305 ℃, and soaking time is 70 minutes in the stove, makes ammonium paratungstate lose part ammonia and crystal water, is converted into ammonium metawolframate soluble in water.Be incubated sampling in 40 minutes and carry out the poach check, solution pH value 4.5, dissolution rate are 75.8%, are incubated 70 minutes sampling boiling tests, solution pH value 3.6, and dissolution rate reaches 93.6%, and stopped heating will be calcined material and be cooled to room temperature, and it is stand-by to come out of the stove.
(2) poach dissolving ammonium metawolframate
Be to add 800 liters in water in 1000 liters the enamel evaporative crystallization still to volume, be heated to and boil that under agitation slowly add 1500 kilograms of calcining material, the control temperature is incubated little digestion of boiling at 85～100 ℃, adds the moisture content of evaporation, substantially keeps original volume.The digestion time is 120 minutes, and minute 3 sub-samplings check pH value is that digestion was checked in the time of 60 minutes for the first time, pH value is 4.7, is that digestion was checked in the time of 90 minutes for the second time, and pH value is 4.1, that digestion was checked in the time of 120 minutes for the third time, pH value is 3.4, this moment stopped heating, filtered while hot, filter residue hot water wash 3～4 times, filtrate is ammonium metatungstate solution, changes ammonium metatungstate solution over to and leaves standstill groove, leaves standstill after 24 hours stand-by.Filter residue is the excessive Tungsten oxide 99.999 of calcining, returns the ammoniacal liquor pressure after the collection and boils again recovery.
(3) spray-drying process is produced ammonium metawolframate
Changing the ammonium metatungstate solution after 1800 liters of filtering and standing over to volume is in 2000 liters the enamel evaporative crystallization still, be heated to boil and keep the boiling, evaporation concentration is to solution proportion 1.4, stopped heating, while hot concentrated solution is pumped into the spray-drier spraying drying, make ammonium metatungstate crystal, be the finished product ammonium metawolframate through check, packing.
Claims (3)
1. process the method that waste and old Tungsten oxide 99.999 is produced ammonium tungstate for one kind, comprise with ammoniacal liquor and press Tungsten oxide 99.999s such as boiling dissolving tungstic oxide, blue tungsten oxide, make wherein a kind of such as ammonium tungstate solution, ammonium paratungstate, ammonium metawolframate, it is characterized in that pressing with ammoniacal liquor and boil dissolved oxygen tungsten and make ammonium tungstate solution.
2. a kind of method that waste and old Tungsten oxide 99.999 is produced ammonium tungstate of processing according to claim 1 is characterized in that boiling the vapor pressure of dissolved oxygen tungsten at 0.5kg/cm with the ammoniacal liquor pressure
2More than, wherein with 4～10kg/cm
2The most suitable.
3. a kind of method that waste and old Tungsten oxide 99.999 is produced ammonium tungstate of processing according to claim 1 and 2 is characterized in that pressing the pressure time of boiling of boiling dissolved oxygen tungsten with ammoniacal liquor is 10～300 minutes, and is wherein suitable with 60～180 minutes.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265080A (en) * | 2013-06-04 | 2013-08-28 | 广东翔鹭钨业股份有限公司 | Method for producing high-purity ammonium paratungstate from tungsten waste |
| CN106395906A (en) * | 2016-10-27 | 2017-02-15 | 江西稀有金属钨业控股集团有限公司 | Method and system for preparing ammonium metatungstate from tungsten oxide waste |
| CN106555061A (en) * | 2016-11-25 | 2017-04-05 | 桂林理工大学 | A kind of quick dissolution method of ammonium paratungstate/Tungstic anhydride. |
| CN109455762A (en) * | 2018-12-04 | 2019-03-12 | 内蒙古佳瑞米精细化工有限公司 | A method of artificial schellite is prepared using chloro-pyridine tar |
| CN109761283A (en) * | 2019-03-20 | 2019-05-17 | 江西省鑫盛钨业有限公司 | A kind of technique for the restoring tungsten oxide handling waste tungsten oxide |
| CN110817963A (en) * | 2019-10-23 | 2020-02-21 | 江西铜鼓有色冶金化工有限责任公司 | Method and system for preparing ammonium metatungstate from acid-soluble slag waste |
| CN111517367A (en) * | 2020-04-07 | 2020-08-11 | 厦门钨业股份有限公司 | Method for preparing high-purity ammonium paratungstate |
| CN111960469A (en) * | 2020-07-30 | 2020-11-20 | 湖南信力新材料有限公司 | Method for producing ammonium paratungstate by using tungsten-containing waste |
| CN114031117A (en) * | 2021-11-17 | 2022-02-11 | 云南锡业集团（控股）有限责任公司研发中心 | Device for continuously preparing high-purity ammonium paratungstate and using method |
| CN114917757A (en) * | 2022-06-13 | 2022-08-19 | 赣州海盛钨业股份有限公司 | Preparation system of high solubility ammonium metatungstate |
| CN115784311A (en) * | 2022-11-24 | 2023-03-14 | 赣州市光华有色金属有限公司 | Method for recycling tungsten oxide through tungsten oxide waste |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265080A (en) * | 2013-06-04 | 2013-08-28 | 广东翔鹭钨业股份有限公司 | Method for producing high-purity ammonium paratungstate from tungsten waste |
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| CN106555061A (en) * | 2016-11-25 | 2017-04-05 | 桂林理工大学 | A kind of quick dissolution method of ammonium paratungstate/Tungstic anhydride. |
| CN109455762A (en) * | 2018-12-04 | 2019-03-12 | 内蒙古佳瑞米精细化工有限公司 | A method of artificial schellite is prepared using chloro-pyridine tar |
| CN109761283A (en) * | 2019-03-20 | 2019-05-17 | 江西省鑫盛钨业有限公司 | A kind of technique for the restoring tungsten oxide handling waste tungsten oxide |
| CN110817963A (en) * | 2019-10-23 | 2020-02-21 | 江西铜鼓有色冶金化工有限责任公司 | Method and system for preparing ammonium metatungstate from acid-soluble slag waste |
| CN111517367A (en) * | 2020-04-07 | 2020-08-11 | 厦门钨业股份有限公司 | Method for preparing high-purity ammonium paratungstate |
| CN111960469A (en) * | 2020-07-30 | 2020-11-20 | 湖南信力新材料有限公司 | Method for producing ammonium paratungstate by using tungsten-containing waste |
| CN114031117A (en) * | 2021-11-17 | 2022-02-11 | 云南锡业集团（控股）有限责任公司研发中心 | Device for continuously preparing high-purity ammonium paratungstate and using method |
| CN114031117B (en) * | 2021-11-17 | 2023-12-01 | 云南锡业集团（控股）有限责任公司研发中心 | Device for continuously preparing high-purity ammonium paratungstate and application method |
| CN114917757A (en) * | 2022-06-13 | 2022-08-19 | 赣州海盛钨业股份有限公司 | Preparation system of high solubility ammonium metatungstate |
| CN115784311A (en) * | 2022-11-24 | 2023-03-14 | 赣州市光华有色金属有限公司 | Method for recycling tungsten oxide through tungsten oxide waste |
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Application publication date: 20130227 |