CN103233125A - Method for extracting tungsten, molybdenum and rhenium from waste high-temperature alloy - Google Patents
Method for extracting tungsten, molybdenum and rhenium from waste high-temperature alloy Download PDFInfo
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- CN103233125A CN103233125A CN2013101392956A CN201310139295A CN103233125A CN 103233125 A CN103233125 A CN 103233125A CN 2013101392956 A CN2013101392956 A CN 2013101392956A CN 201310139295 A CN201310139295 A CN 201310139295A CN 103233125 A CN103233125 A CN 103233125A
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Abstract
The invention discloses a method for extracting tungsten, molybdenum and rhenium from waste high-temperature alloy, which comprises the following steps: carrying out atomization and powder spraying on waste high-temperature alloy containing nickel and cobalt to obtain waste high-temperature alloy particles, carrying out acid leaching on nickel, cobalt and other soluble alloy components in the waste high-temperature alloy particles, washing the leached slag repeatedly to obtain a tungsten-molybdenum-rhenium enriched material; and adding acid, oxidizer and ion exchanger into the tungsten-molybdenum-rhenium enriched material to carry out leaching, and after the reaction finishes, carrying out hot filtration to obtain a solution containing tungsten, molybdenum and rhenium. The method disclosed by the invention uses waste high-temperature alloy as the raw material, is convenient for large-scale production, is a sustainable green way for cyclic utilization of resources, has high practicality and favorable economic prospects, and can generate favorable social benefits.
Description
Technical field
The invention belongs to the hydrometallurgy field, relate to a kind of method of extracting tungsten, molybdenum, rhenium, particularly relate to a kind of method of from waste and old superalloy, extracting tungsten, molybdenum, rhenium.
Background technology
The Mineral resources of waste and old hot metals such as nickel, cobalt, tungsten, molybdenum, rhenium are fewer and feweri, but domestic demand is increasing, thereby will strengthen the reclaiming technology of waste and old superalloy.At present, handle waste and old superalloy and mainly adopt pyrorefining and wet separation purification and pyrogenic process and wet method process combined technology.
Thermal process mainly is by adopting surface treatment and vacuum-oxygen decarbonizing technology (VOD), and in conjunction with the application of regenerating of advanced smelting equipments such as vacuum induction furnace, electroslag furnace with the superalloy waste material.Utilize pollution-free cleaning, the Argon degassing to go slag inclusion, extraordinary slag system to go a series of pureization technology such as inclusion, high vacuum purification to realize the regeneration of superalloy waste material.Thermal process has efficient height, short, the advantages of environment protection of flow process, but has problems such as investment is big, cost height.For example, adopt pyrorefining to handle waste and old superalloy, at first will sort out according to alloy designations these waste materials, by the ultrasonic washing cleaning, remove alloy surface coating by methods such as sandblastings then again, carry out pyrorefining at last again and purify.Adopt this kind method to need substantial contribution to buy sonic cleaning equipment, vacuum melting and equipment for purifying, be typical investment-intensive method, and there is the energy consumption height in this method, is difficult to remove the detrimental impurity in the waste material fully and the shortcomings such as superalloy waste material that influence superalloy performance and work-ing life, can not treatment types mix.
Wet processing is to soak and allow the metal of recovery value enter the chemical process that solution adopts one or more separate modes in chemical precipitation, electrolytic deposition, organic solvent extraction, substitution method, the ion exchange method that the rare precious metal element is separated again with the form of ion carrying out acidleach, alkali after the waste and old superalloy pre-treatment.Wet processing is handled waste and old superalloy and is had that investment is little, energy consumption is low, pollute little and added value of product advantages of higher, and particularly this class hydrometallurgy flow process also can be taken into account the purification of metallic element.
For example: DE 10155791C 1 discloses the method for the waste and old superalloy of a kind of electrochemical treatment, and this method at first with the casting of superalloy waste material in flakes, is carried out electrochemical treatment then in the anaerobic mineral acid.As everyone knows, anode passivation usually taking place in the electrochemical treatment process, stops proceeding of electrolysis.Though can be by in electrolyte solution, adding a certain amount of water or solving the anode passivation problem with certain frequency conversion Faradaic current polarity, but electrochemical process intractable large size waste material also needs the long period even handle some less superalloy fragments.As the content of putting down in writing among the disclosed patent CN1418985A in 2003 05 month 21 days, the superalloy fragment of electrochemical treatment 10.4Kg is wanted the time more than 25 hours at least, visible electrochemical process handle the superalloy waste material industrial be infeasible.
In sum, above method exists long, problems such as energy consumption is high, efficient is low, cost is high, contaminate environment of dissolving cycle.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, a kind of method of extracting tungsten, molybdenum, rhenium from waste and old superalloy is provided, its method steps is simple, it is convenient to realize, input cost is lower and required time is short, result of use is good, can solve effectively that the input cost that existing superalloy waste material recovery method exists is big, loaded down with trivial details, the required treatment time of operating process is long, the rate of recovery is low, be difficult for problem such as industrialization.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of extracting tungsten, molybdenum, rhenium from waste and old superalloy is characterized in that following concrete steps are as follows:
(1) atomizing is dusted:
Adopt atomising method, the waste and old superalloy that will contain tungsten, molybdenum, rhenium is atomized into the superalloy particle that particle diameter is 300 μ m～740 μ m;
(2) selectivity leaches
Nickel cobalt base superalloy particle with waste and old tungstenic, molybdenum, rhenium is raw material, adopts acidleach to leach alloying constituents such as soluble nickel cobalt, and leached mud repeatedly washs and obtains tungsten, molybdenum, rhenium enrichment material and nickel and cobalt solution;
(3) oxidizing acid is molten: tungsten, molybdenum, rhenium enrichment material are added acid, oxygenant, ion-exchanger, under 30～80 ℃ of temperature, leach, and extraction time 3 ~ 10h, heat filtering after reaction is finished obtains tungstenic, molybdenum, rhenium solution.
The material that the present invention uses is the waste and old superalloy that contains the tungsten rhenium.
The acid that the present invention uses is 1:1～3 as one or more mixing in hydrochloric acid, sulfuric acid, the nitric acid, amount ratio;
The oxygenant that the present invention uses is 1:1～3 as one or more mixing in hydrogen peroxide, potassium hypochlorite, the potassium permanganate, amount ratio;
The ion-exchanger that the present invention uses is 1:0.2～0.5 as one or both mixing in ferric sesquichloride, the ferric sulphate, amount ratio.
The technical indicator that the present invention obtains:
(1) tungstenic, molybdenum, rhenium enrichment material tungsten, molybdenum, rhenium content are greater than 79%;
(2) rate of recovery of tungsten, molybdenum, rhenium is greater than 99.5%.
Advantage of the present invention mainly is: technology is simple, low cost, high efficiente callback tungsten, molybdenum, rhenium.Adopt the inventive method, selectivity leaches to be reflected at not to be had waste gas and discharges in the closed reactor, improved labor condition, has reduced cost, tungsten, molybdenum, rhenium almost all enter solution, the direct yield of tungsten, molybdenum, rhenium is greater than 99.5%.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
For better understanding the present invention, below in conjunction with the drawings and specific embodiments the present invention is described in further detail.But the scope of protection of present invention is not limited to the scope of case representation.
Embodiment 1, referring to accompanying drawing 1, and the first step: adopt concrete steps (1) and (2) to obtain tungstenic, molybdenum, rhenium enrichment material, experiment takes by weighing tungsten, molybdenum, the rhenium enrichment material of 100g, adds water 200ml, hydrochloric acid 100ml, hydrogen peroxide 100ml, ferric sesquichloride 20g, stirring velocity 400 r/min, 50 ℃ of temperature, reaction times 10h, reaction finishes back washing five times, each water 300mL, amount of filtrate volume, slag dry for standby, through leaching, filter and washing, the direct yield of tungsten, molybdenum, rhenium is greater than 99.5%.
Embodiment 2, referring to accompanying drawing 1, and the first step: adopt concrete steps (1) and (2) to obtain tungstenic, molybdenum, rhenium enrichment material, experiment takes by weighing tungsten, molybdenum, the rhenium enrichment material of 100g, adds water 200ml, hydrochloric acid 200ml, hydrogen peroxide 200ml, ferric sesquichloride 30g, stirring velocity 400 r/min, 50 ℃ of temperature, reaction times 10h, reaction finishes back washing five times, each water 300mL, amount of filtrate volume, slag dry for standby, through leaching, filter and washing, the direct yield of tungsten, molybdenum, rhenium is greater than 99.5%.
Embodiment 3, referring to accompanying drawing 1, and the first step: adopt concrete steps (1) and (2) to obtain tungstenic, molybdenum, rhenium enrichment material, experiment takes by weighing tungsten, molybdenum, the rhenium enrichment material of 100g, adds water 200ml, hydrochloric acid 300ml, hydrogen peroxide 300ml, ferric sesquichloride 40g, stirring velocity 400 r/min, 50 ℃ of temperature, reaction times 10h, reaction finishes back washing five times, each water 300mL, amount of filtrate volume, slag dry for standby, through leaching, filter and washing, the direct yield of tungsten, molybdenum, rhenium is greater than 99.5%.
Embodiment 4, referring to accompanying drawing 1, and the first step: adopt concrete steps (1) and (2) to obtain tungstenic, molybdenum, rhenium enrichment material, experiment takes by weighing tungsten, molybdenum, the rhenium enrichment material of 100g, adds water 200ml, hydrochloric acid 100ml, hydrogen peroxide 100ml, ferric sesquichloride 50g, stirring velocity 400 r/min, 50 ℃ of temperature, reaction times 10h, reaction finishes back washing five times, each water 300mL, amount of filtrate volume, slag dry for standby, through leaching, filter and washing, the direct yield of tungsten, molybdenum, rhenium is greater than 99.5%.
Claims (7)
1. method of from waste and old superalloy, extracting tungsten, molybdenum, rhenium, it is characterized in that: the waste and old superalloy atomizing earlier that will contain the nickel cobalt is dusted, obtain waste and old superalloy particle, adopt in the waste and old superalloy particle of acidleach alloying constituents such as soluble nickel cobalt, leached mud repeatedly washs and obtains tungsten, molybdenum, rhenium enrichment material; Then tungsten, molybdenum, rhenium enrichment material are added acid, oxygenant, ion-exchanger leaching, leach under 30 ~ 80 ℃ of temperature, extraction time 3 ~ 10h, heat filtering after reaction is finished obtains tungstenic, molybdenum, rhenium solution.
2. according to the described a kind of method of extracting tungsten, molybdenum, rhenium from waste and old superalloy of claim 1, it is characterized in that: concrete steps are as follows:
(1) atomizing is dusted:
Adopt atomising method, the waste and old superalloy that will contain tungsten, molybdenum, rhenium is atomized into the superalloy particle that particle diameter is 300 μ m～740 μ m;
(2) selectivity leaches
Nickel cobalt base superalloy particle with waste and old tungstenic, molybdenum, rhenium is raw material, adopts acidleach to leach alloying constituents such as soluble nickel cobalt, and leached mud repeatedly washs and obtains tungsten, molybdenum, rhenium enrichment material and nickel and cobalt solution;
(3) oxidizing acid is molten: tungsten, molybdenum, rhenium enrichment material are added acid, oxygenant, ion-exchanger, under 30～80 ℃ of temperature, leach, and extraction time 3～10h, heat filtering after reaction is finished obtains tungstenic, molybdenum, rhenium solution.
3. according to the described a kind of method of from waste and old superalloy, extracting tungsten, molybdenum, rhenium of claim 2,
It is characterized in that: the atomizing spraying powder method that adopts in the step (1) is water atomization powder injection process or aerosolization powder injection process or water, gas combined atomising powder injection process.
4. according to the described a kind of method of extracting tungsten, molybdenum, rhenium from waste and old superalloy of claim 2, it is characterized in that: in the tungsten that step (2) is prepared, molybdenum, the rhenium enrichment material, tungsten, molybdenum, rhenium total content are 79 ~ 81%.
5. according to the described a kind of method of extracting tungsten, molybdenum, rhenium from waste and old superalloy of claim 2, it is characterized in that: in the step (3), used acid is one or more mixing in hydrochloric acid, sulfuric acid, the nitric acid, and amount ratio is 1:1～3.
6. according to the described a kind of method of from waste and old superalloy, extracting tungsten, molybdenum, rhenium of claim 2, it is characterized in that: in the step (3), used oxygenant is one or more mixing in hydrogen peroxide, potassium hypochlorite, the potassium permanganate, and amount ratio is 1:1～3.
7. according to the described a kind of method of from waste and old superalloy, extracting tungsten, molybdenum, rhenium of claim 2, it is characterized in that: in the step (3), used ion-exchanger is one or both mixing in ferric sesquichloride, the ferric sulphate, and amount ratio is 1:0.2～0.5.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104164567A (en) * | 2014-08-06 | 2014-11-26 | 贵研铂业股份有限公司 | Method for enriching and recycling niobium and tantalum from waste high-temperature alloy |
| RU2548540C1 (en) * | 2013-12-02 | 2015-04-20 | Александр Александрович Перфилов | Hot gas collecting device |
| CN105714123A (en) * | 2016-05-04 | 2016-06-29 | 中条山有色金属集团有限公司 | Method for preparing ammonium rhenate from rhenium-rich slag |
| CN105983707A (en) * | 2015-01-27 | 2016-10-05 | 昆明冶金高等专科学校 | Method for preparing high-purity rhenium powder from rhenium-containing high-arsenic copper sulfide |
| RU2644641C1 (en) * | 2016-09-29 | 2018-02-13 | Акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method for separating rhenium compounds and related elements from volcanic gases |
| CN110066927A (en) * | 2019-05-27 | 2019-07-30 | 兰州理工大学 | A kind of hydrometallurgic recovery method of bulk high-temperature alloy waste material |
| CN111304446A (en) * | 2020-03-31 | 2020-06-19 | 中国科学院金属研究所 | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching |
| CN111334666A (en) * | 2020-03-31 | 2020-06-26 | 中国科学院金属研究所 | Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste |
| CN111410240A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院金属研究所 | Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste |
| CN114196832A (en) * | 2021-12-16 | 2022-03-18 | 合肥工业大学 | Method for preparing rhenium powder by recycling tungsten-rhenium alloy waste |
| CN114574700A (en) * | 2020-12-02 | 2022-06-03 | 周卓煇 | Method for extracting tungsten oxide from tungsten waste |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343774A (en) * | 1979-08-20 | 1982-08-10 | Union Oil Company Of California | Method for recovering valuable metals from deactivated catalysts |
| CN102560102A (en) * | 2012-01-18 | 2012-07-11 | 长沙矿冶研究院有限责任公司 | Method for leaching nickel and molybdenum from nickel-molybdenum ores by catalytic oxidation |
| CN102978406A (en) * | 2012-12-14 | 2013-03-20 | 西北有色金属研究院 | Regeneration method for rhenium-containing high-temperature alloy scrap |
| CN102994760A (en) * | 2012-12-14 | 2013-03-27 | 西北有色金属研究院 | Regeneration method of high-temperature alloy wastes without rhenium |
-
2013
- 2013-04-22 CN CN2013101392956A patent/CN103233125A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343774A (en) * | 1979-08-20 | 1982-08-10 | Union Oil Company Of California | Method for recovering valuable metals from deactivated catalysts |
| CN102560102A (en) * | 2012-01-18 | 2012-07-11 | 长沙矿冶研究院有限责任公司 | Method for leaching nickel and molybdenum from nickel-molybdenum ores by catalytic oxidation |
| CN102978406A (en) * | 2012-12-14 | 2013-03-20 | 西北有色金属研究院 | Regeneration method for rhenium-containing high-temperature alloy scrap |
| CN102994760A (en) * | 2012-12-14 | 2013-03-27 | 西北有色金属研究院 | Regeneration method of high-temperature alloy wastes without rhenium |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2548540C1 (en) * | 2013-12-02 | 2015-04-20 | Александр Александрович Перфилов | Hot gas collecting device |
| CN104164567A (en) * | 2014-08-06 | 2014-11-26 | 贵研铂业股份有限公司 | Method for enriching and recycling niobium and tantalum from waste high-temperature alloy |
| CN105983707A (en) * | 2015-01-27 | 2016-10-05 | 昆明冶金高等专科学校 | Method for preparing high-purity rhenium powder from rhenium-containing high-arsenic copper sulfide |
| CN105983707B (en) * | 2015-01-27 | 2019-02-15 | 昆明冶金高等专科学校 | A method of high-purity rhenium powder is prepared from rhenium-containing high arsenic-and copper-bearing sulfide |
| CN105714123A (en) * | 2016-05-04 | 2016-06-29 | 中条山有色金属集团有限公司 | Method for preparing ammonium rhenate from rhenium-rich slag |
| RU2644641C1 (en) * | 2016-09-29 | 2018-02-13 | Акционерное общество "Ведущий научно-исследовательский институт химической технологии" | Method for separating rhenium compounds and related elements from volcanic gases |
| CN110066927A (en) * | 2019-05-27 | 2019-07-30 | 兰州理工大学 | A kind of hydrometallurgic recovery method of bulk high-temperature alloy waste material |
| CN111304446A (en) * | 2020-03-31 | 2020-06-19 | 中国科学院金属研究所 | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching |
| CN111334666A (en) * | 2020-03-31 | 2020-06-26 | 中国科学院金属研究所 | Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste |
| CN111410240A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院金属研究所 | Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste |
| CN114574700A (en) * | 2020-12-02 | 2022-06-03 | 周卓煇 | Method for extracting tungsten oxide from tungsten waste |
| CN114196832A (en) * | 2021-12-16 | 2022-03-18 | 合肥工业大学 | Method for preparing rhenium powder by recycling tungsten-rhenium alloy waste |
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Application publication date: 20130807 |