CN103422114A - Preparation method for potassium metavanadate - Google Patents
Preparation method for potassium metavanadate Download PDFInfo
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- CN103422114A CN103422114A CN2012101495869A CN201210149586A CN103422114A CN 103422114 A CN103422114 A CN 103422114A CN 2012101495869 A CN2012101495869 A CN 2012101495869A CN 201210149586 A CN201210149586 A CN 201210149586A CN 103422114 A CN103422114 A CN 103422114A
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Abstract
The invention discloses a preparation method for potassium metavanadate. The preparing method comprises the steps: a potassium vanadate solution as an anode electrolyte solution is subjected to ionic membrane electrolysis, a potassium metavanadate solution with a pH value of 7.0-8.0 and the molar ratio between potassium and vanadium being 0.95-1.05 according to potassium element and vanadium element is obtained at an anode under the ionic membrane electrolysis condition. According to the preparation method of potassium metavanadate, vanadium pentoxide does not need to be firstly prepared, potassium metavanadate can be directly prepared by the potassium vanadate solution, and thus the production steps are simplified; moreover, because sulfuric acid does not need to be employed to adjust the pH value and ammonium sulfate does not need to be employed to precipitate ammonium vanadate, vanadium precipitation wastewater containing potassium sulfate and ammonium sulfate is not produced, and thus the burden on the environment is reduced; and because the vanadium precipitation wastewater containing potassium sulfate and ammonium sulfate is not produced, the vanadium precipitation wastewater does not need to be processed, and thus the production cost is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of potassium metavanadate.
Background technology
Potassium metavanadate (potassium vanadate), molecular formula is KVO
3, molecular mass 138.04,520 ℃ of fusing points, the slightly faint yellow crystalline particle of the white that outward appearance is non-crystallizable.Potassium metavanadate is mainly as chemical reagent, catalyzer, siccative, mordant etc.
The preparation method of existing potassium metavanadate, usually first by containing vanadium minerals, preparing highly purified Vanadium Pentoxide in FLAKES, and then be dissolved in Vanadium Pentoxide in FLAKES in highly purified potassium hydroxide solution, through evaporation concentration, crystallization, obtains the potassium metavanadate product.The preparation process of Vanadium Pentoxide in FLAKES is: will obtain alkaline sodium vanadate solution containing the water logging of vanadium minerals process sodium roasting; Alkaline sodium vanadate solution is carried out to purification and impurity removal and obtain alkaline vanadic acid sodium qualifying liquid; Add ammonium salt precipitation ammonium vanadate in alkaline vanadic acid sodium qualifying liquid after, ammonium vanadate is carried out to the oxidizing roasting decomposition and obtain high-purity vanadium pentoxide.In alkaline vanadic acid sodium qualifying liquid, precipitate in the process of ammonium vanadate, need to add the sulphur acid for adjusting pH value, then add the ammonium sulfate precipitation ammonium vanadate, precipitation obtains ammonium vanadate and vanadium wastewater, contain a small amount of vanadium in vanadium wastewater and reduced the rate of recovery of vanadium, and, owing to adopting sulphur acid for adjusting pH value and ammonium sulfate precipitation ammonium vanadate, make in vanadium wastewater and contain a large amount of sodium sulfate and ammonium sulfate, thereby increased the burden of environment, and increased the processing cost of vanadium wastewater.Therefore, existing technique exists that step is numerous and diverse, the vanadium loss is large, production cost is high, the wastewater treatment difficulty large, to distinct issues such as environment are unfriendly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new potassium metavanadate.The preparation method of potassium metavanadate provided by the invention, not only step is simple, cost is low, and environmentally friendly.
The present inventor, dexterously by carry out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, has reduced the pH value, thereby has obtained highly purified potassium metavanadate solution in de-potassium.And preferably the potassium metavanadate solution obtained is carried out to condensing crystal, thereby obtain highly purified potassium metavanadate.
To achieve these goals, the invention provides a kind of preparation method of potassium metavanadate, wherein, the method comprises carries out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, the condition of electrolysis with ion-exchange film makes to obtain the pH value for 7.0-8.0 at anode, and in potassium element and v element, the potassium metavanadate solution that the mol ratio of potassium and vanadium is 0.95-1.05.
Preparation method according to potassium metavanadate of the present invention, by carry out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, slough superfluous potassium ion by electrolysis with ion-exchange film, reach the pH value that the potassium ion for preparing potassium metavanadate required and reduced simultaneously solution, thereby, without first preparing Vanadium Pentoxide in FLAKES, just can directly by potassium vanadate solution, prepare potassium metavanadate, simplified production stage; And due to without adopting sulphur acid for adjusting pH value and ammonium sulfate precipitation ammonium vanadate, therefore do not produce the vanadium wastewater that contains vitriolate of tartar and ammonium sulfate, reduced the burden of environment; Owing to not producing the vanadium wastewater that contains vitriolate of tartar and ammonium sulfate, thereby without vanadium wastewater is processed, thereby production cost reduced.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to potassium metavanadate preparation method of the present invention, the method comprises carries out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, the condition of electrolysis with ion-exchange film makes to obtain the pH value for 7.0-8.0 at anode, and in potassium element and v element, the potassium metavanadate solution that the mol ratio of potassium and vanadium is 0.95-1.05.
In the present invention, to potassium vanadate solution, there is no particular limitation, as long as meet vanadium concentration in potassium vanadate solution, is 20-35g/L; The pH value is 9-14; In potassium element and v element, the potassium in potassium vanadate solution and the mol ratio of vanadium are that 1.5-2.5 gets final product.Under preferable case, meeting vanadium concentration in potassium vanadate solution is 25-35g/L; The pH value is 10.5-12; In potassium element and v element, the potassium in potassium vanadate solution and the mol ratio of vanadium are 1.5-1.8.
In the present invention, above-mentioned potassium vanadate solution can be the solution that vanadium raw materials is obtained through potassium roasting, water logging.After the method for the potassium vanadate solution that vanadium raw materials is obtained through potassium roasting, water logging can be carried out roasting by vanadium raw materials and sylvite, then the product after the roasting that is soaked in water.Described vanadium raw materials can be for vanadium slag, navajoite with containing one or more in the vanadium waste; Described sylvite can be one or more in potassium hydroxide, salt of wormwood and Repone K.In addition, the condition of potassium roasting and water logging can be identical with the condition of sodium roasting, water logging sodium vanadate solution processed.The condition of sodium roasting, water logging sodium vanadate solution processed is well known in the art.
Particularly, described potassium calcining process can mix described vanadium raw materials and described sylvite, and the compound obtained is sent in stoving oven and carried out the potassium roasting.The ratio of described vanadium raw materials and sylvite can for example, be carried out appropriate selection according to the content (, the content of Vanadium in Vanadium Residue) of vanadium in the kind of selected sylvite and described vanadium raw materials.Usually, the mol ratio of vanadium of element of take in described sylvite and described vanadium raw materials can be 1.1-1.8:1.Preferably, the mol ratio of vanadium of element of take in described sylvite and described vanadium raw materials is 1.2-1.8:1.More preferably, the mol ratio of vanadium of element of take in described sylvite and described vanadium raw materials is 1.4-1.6:1.
In the present invention, the temperature in described stoving oven can be in the scope of 600-850 ℃, preferably in the scope of 600-800 ℃, more preferably in the scope of 720-800 ℃, further preferably in the scope of 740-780 ℃.The residence time of described compound in described stoving oven is so that described compound can be turned to standard by abundant potassium.Preferably, the residence time of described compound in described stoving oven can be 40-120 minute, is preferably 40-90 minute, more preferably 50-70 minute.In addition, described potassium roasting can be carried out in the various stoving ovens commonly used in this area.For example: described potassium roasting can be carried out in multiple hearth furnace or rotary kiln.
The described water logging operation potassium product of roasting that can be soaked in water, thus by vanadium, the form with water-soluble cpds leaches out from described potassium product of roasting.Described immersion can for example, be carried out at the temperature that is greater than 80 ℃ (: can carry out) under 80-90 ℃, and the time of described immersion can be 20-120 minute.Described leaching is preferably carried out under the condition stirred, thereby can further improve leaching efficiency.
According to the present invention, the method comprises carries out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, by electrolysis with ion-exchange film, slough superfluous potassium ion, reaches the pH value that the potassium ion for preparing potassium metavanadate required and reduced simultaneously solution.And the condition by electrolysis with ion-exchange film is controlled at the pH value of the potassium metavanadate solution that obtains in specific scope, and the mol ratio of the potassium in the potassium metavanadate solution obtained and vanadium is controlled in specific scope, thereby obtains highly purified potassium metavanadate.
In the present invention, it is 7.0-8.0 that the condition of described electrolysis with ion-exchange film makes the pH value of the potassium metavanadate solution that obtains at anode, and, in potassium element and v element, the mol ratio of potassium and vanadium is 0.95-1.05; In order further to improve the potassium metavanadate solution that obtains and the purity of potassium metavanadate, it is 7.0-7.5 that the condition of preferred described electrolysis with ion-exchange film makes the pH value of the potassium metavanadate solution that obtains at anode, and, in potassium element and v element, the mol ratio of potassium and vanadium is 0.98-1.02.
In the present invention, the selectable range of the condition of described electrolysis with ion-exchange film is wider.Under preferable case, the condition of described electrolysis with ion-exchange film comprises: voltage is 5-15V, and electric current is 0.01-1.5A, and electrolysis time is 2-8 hour; More preferably voltage is 10-15V, and electric current is 0.05-1.5A, and electrolysis time is 3-6 hour.
In addition, in described electrolysis with ion-exchange film, preferably catholyte is water or potassium hydroxide solution; Water more preferably.In the present invention, in electrolytic process, potassium ion sees through cationic exchange membrane and moves to cathode compartment, enter the hydroxide ion that the potassium ion of catholyte produces together with negative electrode By Electrolysis water and generate potassium hydroxide, therefore can directly recycle as catholyte of the present invention without any processing.
According to the present invention, the cationic exchange membrane in described electrolysis with ion-exchange film can be this area various ion-exchange membranees commonly used.Such as this ion-exchange membrane, it can be the film made from the anionic functional groups' such as sulfonic group and/or carboxylic acid group (per) fluoropolymer on side chain, the perfluorinated sulfonic acid that perhaps can strengthen for poly-fluorohydrocarbon fabric-perfluorocarboxylic acid composite membrane, and described ion-exchange membrane can be by commercially available.
According to the present invention, described electrolysis with ion-exchange film can be carried out in ion-membrane electrolysis device known in the art, and for example, described ion-membrane electrolysis device generally includes anolyte compartment and the cathode compartment separated by dividing plate; Described anolyte compartment for example can be on the titanium support mesh at the titanium dish, and one deck anode of burn-oning forms anolyte compartment's (by thin, thick shape net and titanium plate, forming anolyte compartment), and the material of anode can be titanium, is mesh-like; Described cathode compartment for example can for the nickel dish the nickel support mesh on, cover the Elasticity Ni that one deck is woven into by nickel wire, on Elasticity Ni, tiling one deck active nickel negative electrode, form cathode compartment (by thick, soft, thin three kinds of cathode compartments that nickel screen forms), the material of negative electrode is nickel, the elasticity nickel screen, consists of.
According to the present invention, under preferable case, the method also comprises carries out condensing crystal by the potassium metavanadate solution obtained, and obtains potassium metavanadate.The method of described condensing crystal and condition are well known in the art.For example, potassium metavanadate solution can be concentrated under 40-95 ℃, be concentrated into that crystal occurs or during 0.1-0.5 times of original solution, temperature dropped to below 40 ℃ and carries out decrease temperature crystalline, also can, after temperature being dropped to below 40 ℃, by standing or stirring, further carry out crystallization.Crystallization obtains potassium metavanadate solid and filtrate by solid-liquid separation.The method of solid-liquid separation is well known in the art, such as filtering, centrifugal etc.
In addition, in the present invention, in order further to reduce costs, above-mentioned filtrate can also be leached to operation (while by vanadium raw materials, preparing potassium vanadate solution) recycle for directly returning.And what generate at negative electrode after electrolysis is potassium hydroxide, can directly recycle as catholyte of the present invention without any processing.
Below will describe the present invention by embodiment, but the present invention is not limited in following embodiment.
In following examples, by by potassium hydroxide with take the mol ratio of vanadium of element after 1.2-1.8:1 is mixed in vanadium slag, carry out roasting 40-90 minute under 600-800 ℃, then, under 80 ℃, after being soaked in water product of roasting 40-100 minute, separate and obtain potassium vanadate solution.
In following examples, the contents on dry basis of potassium metavanadate adopts following measuring method to be measured.
(1) by the potassium metavanadate solid drying that obtains in embodiment to constant weight, as specimen;
(2) with the potassium content in the Atomic Absorption Spectrometry sample;
(3) method of the content of vanadium in working sample is: accurately take specimen 0.25g, add 50ml water, slowly inject 10ml sulfuric acid, heating for dissolving, cooling, add 4 0.1% phenylanthranilic acid ethanolic solns, be titrated to solution with 0.1mol/L ferrous ammonium sulphate standardized solution and become bright green by red-purple.Volume and the concentration of the l ferrous ammonium sulfate solution of then using according to titration are calculated content of vanadium.
(4) calculate the amount of potassium metavanadate in sample according to potassium vanadium mol ratio 1:1;
(5) contents on dry basis of the weight calculating potassium metavanadate of dried potassium metavanadate solid in the amount by potassium metavanadate in sample and step (1).
Embodiment 1
The present embodiment is for illustrating the preparation of potassium metavanadate
At ion-membrane electrolysis device, (be purchased from Di Nuola electrode (Suzhou) company limited, ion-exchange membrane is Nafion117, and anode is the titanium net, and negative electrode is nickel screen; Below identical) in anolyte compartment add potassium vanadate solution (in v element, in potassium vanadate solution, the concentration of vanadium be 30g/L; In potassium element and v element, potassium vanadium mol ratio is 1.5; PH is 12) 500mL, negative electrode adds the water of same volume, and voltage control is at 12V, and electric current is 0.05A, connects DC electrolysis 3 hours, and obtaining pH is 7.0, and in potassium element and v element, the potassium metavanadate solution that potassium vanadium mol ratio is 0.98.After under 80 ℃, the potassium metavanadate solution decompression being concentrated to 100ml, more under agitation be cooled to 25 ℃ of crystallize outs, and filtration obtains the potassium metavanadate solid.The contents on dry basis of the potassium metavanadate obtained is 98.3 % by weight.
Embodiment 2
The present embodiment is for illustrating the preparation of potassium metavanadate
Anolyte compartment in ion-membrane electrolysis device adds potassium vanadate solution, and (in v element, in potassium vanadate solution, the concentration of vanadium is 35g/L; In potassium element and v element, potassium vanadium mol ratio is 1.8; PH is 11.5) 500mL, negative electrode adds the water of same volume, and voltage control is at 15V, and the connection galvanic current is 1.5A, electrolysis 5 hours, obtaining pH is 7.2, and in potassium element and v element, the potassium metavanadate solution that potassium vanadium mol ratio is 0.99.After under 80 ℃, the potassium metavanadate solution decompression being concentrated to 100ml, more under agitation be cooled to 25 ℃ of crystallize outs, and filtration obtains the potassium metavanadate solid.The contents on dry basis of the potassium metavanadate obtained is 98.6 % by weight.
Embodiment 3
The present embodiment is for illustrating the preparation of potassium metavanadate
Anolyte compartment in ion-membrane electrolysis device adds potassium vanadate solution, and (in v element, in potassium vanadate solution, the concentration of vanadium is 25g/L; In potassium element and v element, potassium vanadium mol ratio is 1.6; PH is 10.5) 500mL, negative electrode adds the water of same volume, and voltage control is at 12V, and the connection galvanic current is 1.0A, electrolysis 6 hours, obtaining pH is 7.5, and in potassium element and v element, the potassium metavanadate solution that potassium vanadium mol ratio is 1.02.After under 80 ℃, the potassium metavanadate solution decompression being concentrated to 100ml, more under agitation be cooled to 25 ℃ of crystallize outs, and filtration obtains the potassium metavanadate solid.The contents on dry basis of the potassium metavanadate obtained is 98.5 % by weight.
Embodiment 4
The present embodiment is for illustrating the preparation of potassium metavanadate
Method according to embodiment 3 is carried out, and different is the potassium hydroxide solution that negative electrode adds 10 % by weight of same volume, and voltage control is at 5V, the connection galvanic current is 0.05A, electrolysis 8 hours, and obtaining pH is 8.0, and in potassium element and v element, the potassium metavanadate solution that potassium vanadium mol ratio is 1.05.After under 80 ℃, the potassium metavanadate solution decompression being concentrated to 100ml, more under agitation be cooled to 25 ℃ of crystallize outs, and filtration obtains the potassium metavanadate solid.The contents on dry basis of the potassium metavanadate obtained is 98.1 % by weight.
Known by embodiment 1-4, adopt electrolysis with ion-exchange film can slough superfluous potassium ion, reach the pH value that the potassium ion for preparing potassium metavanadate required and can reduce simultaneously solution.And, control the pH value of the potassium metavanadate solution obtained by the condition of electrolysis with ion-exchange film in specific scope, and the mol ratio of controlling potassium in the potassium metavanadate solution obtain and vanadium can access the highly purified potassium metavanadate of contents on dry basis more than 98 % by weight in specific scope.
In addition, known by embodiment 1-4, the present invention can directly carry out electrolysis by potassium vanadate solution as anolyte and obtain potassium metavanadate, therefore without first preparing Vanadium Pentoxide in FLAKES, just can directly by potassium vanadate solution, prepare potassium metavanadate, simplify production stage; In addition, due to without adopting sulphur acid for adjusting pH value and ammonium sulfate precipitation ammonium vanadate, therefore do not produce the vanadium wastewater that contains vitriolate of tartar and ammonium sulfate, reduced the burden of environment; Owing to not producing the vanadium wastewater that contains vitriolate of tartar and ammonium sulfate, thereby without vanadium wastewater is processed, thereby production cost reduced.
Claims (9)
1. the preparation method of a potassium metavanadate, it is characterized in that, the method comprises carries out electrolysis with ion-exchange film using potassium vanadate solution as anolyte, the condition of electrolysis with ion-exchange film makes to obtain the pH value for 7.0-8.0 at anode, and in potassium element and v element, the potassium metavanadate solution that the mol ratio of potassium and vanadium is 0.95-1.05.
2. method according to claim 1, wherein, it is 7.0-7.5 that the condition of described electrolysis with ion-exchange film makes the pH value of the potassium metavanadate solution that obtains at anode, and, in potassium element and v element, the mol ratio of potassium and vanadium is 0.98-1.02.
3. method according to claim 1 and 2, wherein, the condition of described electrolysis with ion-exchange film comprises: voltage is 5-15V, and electric current is 0.01-1.5, and electrolysis time is 2-8 hour.
4. method according to claim 3, wherein, the condition of described electrolysis with ion-exchange film comprises: voltage is 12-15V, and electric current is 0.05-1.5A, and electrolysis time is 3-6 hour.
5. method according to claim 1 and 2, wherein, the condition of described electrolysis with ion-exchange film also comprises: catholyte is water or potassium hydroxide solution.
6. method according to claim 1 and 2, wherein, the solution of described potassium vanadate solution for vanadium raw materials is obtained through potassium roasting, water logging.
7. method according to claim 6, wherein, the method that vanadium raw materials is prepared to potassium vanadate solution through potassium roasting, water logging comprises: after vanadium raw materials and sylvite are carried out to roasting, then the product after the roasting that is soaked in water.
8. method according to claim 6, wherein, in v element, in described potassium vanadate solution, vanadium concentration is 25-35g/L; The pH value is 9-14; In potassium element and v element, the potassium in potassium vanadate solution and the mol ratio of vanadium are 1.5-2.5.
9. method according to claim 1, wherein, the method also comprises carries out condensing crystal by the potassium metavanadate solution obtained, and obtains potassium metavanadate.
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Cited By (1)
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| CN104694748A (en) * | 2015-02-04 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for removing sodium or potassium by electrodialysis in vanadium-containing solution |
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| CN101445271A (en) * | 2009-01-04 | 2009-06-03 | 李乾宽 | A method of producing vanadic oxide by using ore containing vanadium or SLAG containing vanadium |
| CN101723455A (en) * | 2009-12-29 | 2010-06-09 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing sodium metavanadate |
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| SU1691424A1 (en) * | 1988-07-26 | 1991-11-15 | Дагестанский Государственный Университет Им.В.И.Ленина | Method for obtaining vanadium oxide(v) |
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| CN101445271A (en) * | 2009-01-04 | 2009-06-03 | 李乾宽 | A method of producing vanadic oxide by using ore containing vanadium or SLAG containing vanadium |
| CN101723455A (en) * | 2009-12-29 | 2010-06-09 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing sodium metavanadate |
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| CN104694748A (en) * | 2015-02-04 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for removing sodium or potassium by electrodialysis in vanadium-containing solution |
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