CN111960469A - Method for producing ammonium paratungstate by using tungsten-containing waste - Google Patents

Method for producing ammonium paratungstate by using tungsten-containing waste Download PDF

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Publication number
CN111960469A
CN111960469A CN202010753591.5A CN202010753591A CN111960469A CN 111960469 A CN111960469 A CN 111960469A CN 202010753591 A CN202010753591 A CN 202010753591A CN 111960469 A CN111960469 A CN 111960469A
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tungsten
stirring
ammonium paratungstate
containing waste
solution
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吴意德
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Hunan Xinli New Material Co ltd
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Hunan Xinli New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of ammonium paratungstate production, in particular to a method for producing ammonium paratungstate by utilizing tungsten-containing waste, which comprises the steps of firstly calcining the tungsten-containing waste and sodium carbonate in a calcining furnace, discharging after agglomeration, grinding and crushing the calcined waste, then placing the crushed powder in a stirring barrel for stirring, boiling and filtering the stirred solution, filtering and removing impurities from the solution after standing through a filter, carrying out evaporative crystallization on the solution after impurity removal by utilizing an evaporative crystallization reaction kettle, then carrying out solid-liquid separation by utilizing a separator to take out ammonium paratungstate crystals, and finally storing the dried ammonium paratungstate in batches. The production and use cost is reduced, and the method has higher practical value and significance.

Description

Method for producing ammonium paratungstate by using tungsten-containing waste
Technical Field
The invention relates to the technical field of ammonium paratungstate production, in particular to a method for producing ammonium paratungstate by utilizing tungsten-containing waste materials.
Background
Tungsten is a strategic metal, rare metals are known to be a significant strategic resource in the country, and tungsten, a typical rare metal, has extremely important uses. It is an important component of modern high-tech new materials, and a series of electron-optical materials, special alloys, novel functional materials, organic metal compounds and the like all need to use tungsten with unique performance. The dosage is not large, but is vital and cannot be used. Therefore, the method is widely applied to modern communication technology, electronic computers, space navigation development, medicine and health, photosensitive materials, photoelectric materials, energy materials, catalyst materials and the like, meanwhile, the ammonium paratungstate is a chemical substance, mainly white crystals, two kinds of flake or needle-shaped materials are provided, the ammonium paratungstate is slightly soluble in water, the solubility in water at 20 ℃ is less than 2 percent, the ammonium paratungstate is insoluble in alcohol, the ammonium paratungstate is heated to 220-280 ℃ to lose part of ammonia and crystal water, the ammonium paratungstate can be converted into ammonium metatungstate AMT, and the total ammonia and crystal water are lost when the ammonium paratungstate is heated to above 600 ℃, the ammonium paratungstate is completely converted into yellow tungsten trioxide, and the method is mainly used for preparing metal tungsten powder from; downstream products of the metal tungsten powder are tungsten material series, such as tungsten bars, tungsten filaments and other electric vacuum materials; there are alloy series, such as tungsten carbide, cemented carbide, alloy blades, alloy bits, alloy dies, etc.; other wear-resistant, pressure-resistant and high-temperature-resistant mechanical equipment parts and the like often generate tungsten-containing waste materials in the production process of ammonium paratungstate, and if the tungsten-containing waste materials are not utilized, the waste of scarce resources is caused, so that the method for producing ammonium paratungstate by utilizing the tungsten-containing waste materials is provided for solving the problems.
Disclosure of Invention
The invention aims to provide a method for producing ammonium paratungstate by utilizing tungsten-containing waste materials, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for producing ammonium paratungstate by using tungsten-containing waste comprises the following steps:
the method comprises the following steps: mixing tungsten-containing waste and sodium carbonate according to the proportion of 1: (0.6-0.9) placing the mixture into a calcining furnace for calcining, keeping a semi-molten state for 4-5 hours, discharging the mixture after agglomeration, grinding and crushing calcined waste into 2000 meshes;
step two: placing the crushed powder in a stirring barrel for stirring, adding concentrated sulfuric acid into the stirring barrel to adjust the pH value to 7-11, stirring for 10-13 minutes at the speed of 600-700 r/min, then increasing the speed to 1200-1500 r/min, stirring for 18-20 minutes, and finally increasing the stirring speed to 2200-2500 r/min, and stirring for 10-15 minutes;
step three: boiling the stirred solution, and then slowly stirring for 0.8-1 hour to keep the temperature of the solution at 20-35 ℃, and filtering the solution to obtain solid impurities and filtrate;
step four: tungsten trioxide is used as an electrode anode, a carbon rod is used as a cathode electrode to carry out electrified electrolytic catalytic reaction for 50-60 minutes, and then the mixture is kept stand for 30 minutes;
step five: filtering the standing solution through a filter to remove impurities, wherein impurities such as silicon, calcium, phosphorus, boron, carbon, arsenic and the like in the solution can be removed;
step six: evaporating and crystallizing the solution after impurity removal by using an evaporation and crystallization reaction kettle, then carrying out solid-liquid separation by using a separator to take out ammonium paratungstate crystals, washing the taken out crystals for 20 minutes by using pure water, and drying;
step seven: the dried ammonium paratungstate was stored in batches.
Preferably, the tungsten-containing waste is leaching slag generated in the production process of ammonium metatungstate and mixed waste generated in the production process of tungsten oxide.
Preferably, the feeding amount of the calcining furnace in the step one is 80-120 kg per hour, and the temperature during the calcining process is 500-.
Preferably, the stirring speed of the slow stirring in the third step is 50-80 revolutions per minute.
Preferably, in the sixth step, the stirring temperature is controlled to be 80-100 revolutions per minute, and the temperature of the reaction kettle is controlled to be 120-150 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, the waste containing tungsten can be utilized, the waste is recycled, the waste of strategic resources is avoided, meanwhile, the utilization rate of tungsten is improved by utilizing the waste containing tungsten to produce ammonium paratungstate, the production flow is shortened, the production and use cost is reduced, and the method has high practical value and significance.
Detailed Description
Example 1:
the invention provides a technical scheme that:
a method for producing ammonium paratungstate by using tungsten-containing waste comprises the following steps:
the method comprises the following steps: mixing tungsten-containing waste and sodium carbonate according to the proportion of 1: 0.6, putting the materials into a calcining furnace for calcining, keeping the materials in a semi-molten state for 4 hours, discharging the materials after agglomeration, controlling the feeding amount of the calcining furnace to be 80 kg per hour, simultaneously controlling the temperature in the calcining process to be 500-DEG C, and then grinding and crushing the waste materials after calcination to 2000 meshes;
step two: placing the crushed powder in a stirring barrel for stirring, adding concentrated sulfuric acid into the stirring barrel to adjust the pH value to 7, stirring for 10 minutes at a speed of 600 revolutions per minute, then increasing the speed to 1200 revolutions per minute, stirring for 18 minutes, and finally increasing the stirring speed to 2200 revolutions per minute, and stirring for 10 minutes;
step three: boiling the stirred solution, and then slowly stirring for 0.8 hour at a stirring speed of 50 revolutions per minute to keep the temperature of the solution at 20 ℃, and filtering the solution to obtain solid impurities and filtrate;
step four: tungsten trioxide is used as an electrode anode, a carbon rod is used as a cathode electrode to carry out electrified electrolytic catalytic reaction, the reaction time is 50 minutes, and then the mixture is kept stand for 30 minutes;
step five: filtering the standing solution through a filter to remove impurities, wherein impurities such as silicon, calcium, phosphorus, boron, carbon, arsenic and the like in the solution can be removed;
step six: carrying out evaporative crystallization on the solution after impurity removal by using an evaporative crystallization reaction kettle, controlling the stirring temperature of the reaction kettle to be 80 revolutions per minute and the temperature of the reaction kettle to be 120 ℃, then carrying out solid-liquid separation by using a separator to take out ammonium paratungstate crystals, washing the taken out crystals for 20 minutes by using pure water, and drying;
step seven: the dried ammonium paratungstate was stored in batches.
Example 2:
the invention provides a technical scheme that:
a method for producing ammonium paratungstate by using tungsten-containing waste comprises the following steps:
the method comprises the following steps: mixing tungsten-containing waste and sodium carbonate according to the proportion of 1: 0.7, putting the materials into a calcining furnace for calcining, wherein the tungsten-containing waste materials are leaching residues generated in the production process of ammonium metatungstate and mixed waste materials generated in the production process of tungsten oxide, keeping the materials in a semi-molten state for 4.5 hours, discharging the materials after agglomeration, controlling the feeding amount of the calcining furnace to be 100 kg per hour, and simultaneously controlling the temperature in the calcining process to be 600 ℃, and then grinding and crushing the waste materials after calcination to 2000 meshes;
step two: placing the crushed powder in a stirring barrel for stirring, adding concentrated sulfuric acid into the stirring barrel to adjust the pH value to 9, stirring for 11 minutes at a speed of 650 revolutions per minute, then increasing the speed to 1300 revolutions per minute, stirring for 19 minutes, and finally increasing the stirring speed to 2300 revolutions per minute, and stirring for 13 minutes;
step three: boiling the stirred solution, and then slowly stirring for 0.9 hour at a stirring speed of 70 revolutions per minute to keep the temperature of the solution at 30 ℃, and filtering the solution to obtain solid impurities and filtrate;
step four: tungsten trioxide is used as an electrode anode, a carbon rod is used as a cathode electrode to carry out electrified electrolytic catalytic reaction, the reaction time is 50 minutes, and then the mixture is kept stand for 30 minutes;
step five: filtering the standing solution through a filter to remove impurities, wherein impurities such as silicon, calcium, phosphorus, boron, carbon, arsenic and the like in the solution can be removed;
step six: carrying out evaporative crystallization on the solution after impurity removal by using an evaporative crystallization reaction kettle, controlling the stirring temperature of the reaction kettle to be 90 revolutions per minute and the temperature of the reaction kettle to be 130 ℃, then carrying out solid-liquid separation by using a separator to take out ammonium paratungstate crystals, washing the taken out crystals for 20 minutes by using pure water, and drying;
step seven: the dried ammonium paratungstate was stored in batches.
Example 3:
the invention provides a technical scheme that: the method comprises the following steps:
the method comprises the following steps: mixing tungsten-containing waste and sodium carbonate according to the proportion of 1: 0.9, putting the materials into a calcining furnace for calcining, keeping the tungsten-containing waste materials as leaching slag generated in the production process of ammonium metatungstate and mixed waste materials generated in the production process of tungsten oxide in a semi-molten state for 5 hours, discharging the materials after agglomeration, controlling the feeding amount of the calcining furnace to be 120 kilograms per hour, and simultaneously controlling the temperature in the calcining process to be 700 ℃, and then grinding and crushing the waste materials after calcination to 2000 meshes;
step two: placing the crushed powder in a stirring barrel for stirring, adding concentrated sulfuric acid into the stirring barrel to adjust the pH value to 11, stirring for 13 minutes at a speed of 700 revolutions per minute, then increasing the speed to 1500 revolutions per minute, stirring for 20 minutes, and finally increasing the stirring speed to 2500 revolutions per minute, and stirring for 15 minutes;
step three: boiling the stirred solution, and then slowly stirring for 1 hour at a stirring speed of 80 revolutions per minute to keep the temperature of the solution at 35 ℃, and filtering the solution to obtain solid impurities and filtrate;
step four: tungsten trioxide is used as an electrode anode, a carbon rod is used as a cathode electrode to carry out electrified electrolytic catalytic reaction, the reaction time is 60 minutes, and then the mixture is kept stand for 30 minutes;
step five: filtering the standing solution through a filter to remove impurities, wherein impurities such as silicon, calcium, phosphorus, boron, carbon, arsenic and the like in the solution can be removed;
step six: carrying out evaporative crystallization on the solution after impurity removal by using an evaporative crystallization reaction kettle, controlling the stirring temperature of the reaction kettle to be 100 revolutions per minute and the temperature of the reaction kettle to be 150 ℃, then carrying out solid-liquid separation by using a separator to take out ammonium paratungstate crystals, washing the taken out crystals for 20 minutes by using pure water, and drying;
step seven: the dried ammonium paratungstate was stored in batches.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.

Claims (5)

1. A method for producing ammonium paratungstate by using tungsten-containing waste is characterized by comprising the following steps:
the method comprises the following steps: mixing tungsten-containing waste and sodium carbonate according to the proportion of 1: (0.6-0.9) placing the mixture into a calcining furnace for calcining, keeping a semi-molten state for 4-5 hours, discharging the mixture after agglomeration, grinding and crushing calcined waste into 2000 meshes;
step two: placing the crushed powder in a stirring barrel for stirring, adding concentrated sulfuric acid into the stirring barrel to adjust the pH value to 7-11, stirring for 10-13 minutes at the speed of 600-700 r/min, then increasing the speed to 1200-1500 r/min, stirring for 18-20 minutes, and finally increasing the stirring speed to 2200-2500 r/min, and stirring for 10-15 minutes;
step three: boiling the stirred solution, and then slowly stirring for 0.8-1 hour to keep the temperature of the solution at 20-35 ℃, and filtering the solution to obtain solid impurities and filtrate;
step four: tungsten trioxide is used as an electrode anode, a carbon rod is used as a cathode electrode to carry out electrified electrolytic catalytic reaction for 50-60 minutes, and then the mixture is kept stand for 30 minutes;
step five: filtering the standing solution through a filter to remove impurities, wherein impurities such as silicon, calcium, phosphorus, boron, carbon, arsenic and the like in the solution can be removed;
step six: evaporating and crystallizing the solution after impurity removal by using an evaporation and crystallization reaction kettle, then carrying out solid-liquid separation by using a separator to take out ammonium paratungstate crystals, washing the taken out crystals for 20 minutes by using pure water, and drying;
step seven: the dried ammonium paratungstate was stored in batches.
2. The method for producing ammonium paratungstate by using tungsten-containing waste material according to claim 1, wherein the method comprises the following steps: the tungsten-containing waste is leaching slag generated in the production process of ammonium metatungstate and mixed waste generated in the production process of tungsten oxide.
3. The method for producing ammonium paratungstate by using tungsten-containing waste material according to claim 1, wherein the method comprises the following steps: the feeding amount of the calcining furnace in the step one is 80-120 kg per hour, and the temperature in the calcining process is 500-700 ℃.
4. The method for producing ammonium paratungstate by using tungsten-containing waste material according to claim 1, wherein the method comprises the following steps: the stirring speed of the slow stirring in the third step is 50-80 revolutions per minute.
5. The method for producing ammonium paratungstate by using tungsten-containing waste material according to claim 1, wherein the method comprises the following steps: in the sixth step, the stirring temperature is controlled to be 80-100 rpm, and the temperature of the reaction kettle is controlled to be 120-150 ℃.
CN202010753591.5A 2020-07-30 2020-07-30 Method for producing ammonium paratungstate by using tungsten-containing waste Pending CN111960469A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN103950984A (en) * 2014-04-23 2014-07-30 湖南顺泰钨业股份有限公司 Method for producing sodium tungstate solution by use of tungsten-containing waste grinding material, and sodium tungstate
CN109019691A (en) * 2018-10-10 2018-12-18 江西省修水赣北钨业有限公司 A kind of preparation process of ammonium paratungstate
CN109796046A (en) * 2019-03-20 2019-05-24 江西省鑫盛钨业有限公司 A kind of preparation process of high-purity ammonium paratungstate
CN110563039A (en) * 2019-09-11 2019-12-13 赣州市海龙钨钼有限公司 Method for preparing ammonium paratungstate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN103950984A (en) * 2014-04-23 2014-07-30 湖南顺泰钨业股份有限公司 Method for producing sodium tungstate solution by use of tungsten-containing waste grinding material, and sodium tungstate
CN109019691A (en) * 2018-10-10 2018-12-18 江西省修水赣北钨业有限公司 A kind of preparation process of ammonium paratungstate
CN109796046A (en) * 2019-03-20 2019-05-24 江西省鑫盛钨业有限公司 A kind of preparation process of high-purity ammonium paratungstate
CN110563039A (en) * 2019-09-11 2019-12-13 赣州市海龙钨钼有限公司 Method for preparing ammonium paratungstate

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Application publication date: 20201120