CN103421953A - Method for deep separation of vanadium and molybdenum - Google Patents
Method for deep separation of vanadium and molybdenum Download PDFInfo
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- CN103421953A CN103421953A CN2013103233085A CN201310323308A CN103421953A CN 103421953 A CN103421953 A CN 103421953A CN 2013103233085 A CN2013103233085 A CN 2013103233085A CN 201310323308 A CN201310323308 A CN 201310323308A CN 103421953 A CN103421953 A CN 103421953A
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- molybdenum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for deep separation of vanadium and molybdenum, which comprises three steps of presetting of the pH value of a solution, adjustment of the ion state and resin ion exchange separation analysis. Firstly, a persulfate solution containing vanadium and molybdenum is adjusted to reach the proper value by using sulfuric acid, the oxidation reduction potential of the solution is adjusted through adding reducing agent and oxidizing agent, the valence states and ionic conditions of vanadium and molybdenum are adjusted, vanadium is reduced into V (IV) from V (V), and exists in the form of VO<2+>, molybdenum exists in the form of sexavalence anion, then obtained solution continuously passes through exchange columns of the strong-base anion exchange resin, the exchange speed is controlled as per the contact time of 20-30 minutes, the adsorption effect is adjusted according to the concentration of Mo of the effluent, and the loaded resin is recycled after being analyzed. The method has the advantages that through changing the existing valence states of vanadium and molybdenum, vanadium and molybdenum exist in different hydrated ion forms and through selective adsorption of the resin, the deep separation of vanadium and molybdenum can be realized.
Description
Technical field:
The present invention relates to the method for vanadium in solution, the separation of the molybdenum degree of depth, the degree of depth containing vanadium, molybdenum solution be specially adapted in the vanadium chemistry production process is separated.
Background technology:
Vanadium is similar because of its chemical property with molybdenum, and when the hydrometallurgical extraction of vanadium, if be accompanied by the existence of molybdenum, both are difficult to separate.Traditional Separation of vanadium and molybdenum method is in the vanadium molybdate solution, to add ammonium salt to make vanadium generate the vanadate precipitation, reaches vanadium molybdate separating effect.This method is applicable to the solution that vanadate concentration is higher, can't realize the thorough separation of vanadium molybdate, and after precipitation, solution still contains the mixing solutions of certain density vanadium molybdate.For the vanadium molybdate solution containing lower concentration, when traditional ion-exchange, vanadate and molybdate can be adsorbed by resin simultaneously, while resolving after resin completes absorption, obtain being still the mixing solutions of vanadium molybdate, can't realize the thorough separation of vanadium molybdenum.
Above traditional method can't realize the thorough separation of vanadium molybdate, and technical process is long, and the vanadium molybdenum recovery is low, can't thoroughly separate.The invention provides a kind of method of vanadium, the separation of the molybdenum solution degree of depth, the vanadium molybdate solution, after pre-treatment, can be realized the thorough separation of vanadium molybdate after primary sorption completes, and technique is simple, and the vanadium molybdenum recovery is high.
Summary of the invention:
The invention provides a kind of degree of depth separation method containing the vanadium molybdate solution.The present invention comprises pH value of solution adjustment, ionic condition adjustment and a resin ion-exchange absorption Annex III step, is achieved through the following technical solutions:
The first step, pH adjusts: containing the vanadium molybdate solution, add the vitriol oil (92.5%) to be adjusted to pH=1-5, measure wherein vanadium and molybdenum concentration.
Second step, ionic condition adjustment: add reductive agent and oxygenant to adjust the redox potential of solution, detect VO
2+And VO
2 +Content, make vanadium with VO
2+The valency form exists, and molybdenum exists with the form of negatively charged ion.
The 3rd step, resin absorption is separated: above-mentioned solution is continuously by filling the exchange column of strongly basic anion exchange resin, exchange velocity by duration of contact 20-30min control, the Mo of take in effluent liquid reaches 0.02g/l as absorption terminal, the i.e. breakthrough point of Mo in adsorption process.Resolve the resin of load Mo to resolve agent, resolution speed, by 40-60min control duration of contact, is effectively resolved the resin of load molybdenum.
Be reduced to+4 valencys of vanadium ion, with VO
2+The hydrated cation form exists.Strongly basic anion exchange resin has very high selectivity to the negatively charged ion in solution, resin absorption molybdenum and do not adsorb vanadium, and effluent liquid is for containing vanadium solution.The resin of resolving the load molybdenum to resolve agent obtains certain density molybdenum solution, and resin, after resolving, can recycle.
The present invention is a kind of method that degree of depth of vanadium molybdate of lower concentration is separated, and can realize that the degree of depth of vanadium molybdenum is separated, and desorbed solution separates without secondary vanadium molybdate, and the organic efficiency of vanadium molybdate is high.Solve that tail washings after traditional Separation of vanadium and molybdenum is processed and the circulation enrichment problem of vanadium molybdate desorbed solution, shortened separating technology, saving material usage quantity.Separate the recycling that has simultaneously realized the lower concentration molybdate, there is certain economic benefit.Embodiment
In conjunction with following instance, invention is further illustrated:
Be mingled with certain molybdenum containing in vanadium raw materials, after traditional hydrometallurgy vanadium extraction finishes, in gained waste water, not only contain vanadium but also contain molybdenum, due to process precipitate A MV, the vanadium concentration of mother liquor reduces, and the vanadium molybdenum is than significantly raising.Therefore by Separation of vanadium and molybdenum, the production of high purity vanadium product is just become to very important.
Embodiment 1:
Get 3.5L containing vanadium, molybdenum solution V
2O
5=1.68g/l, Mo=0.51g/l, stir and to add sulfuric acid to adjust pH to 3, adds hydrogen peroxide to adjust current potential to 580mv, is stirred to stablely, with flow velocity and the 100ml resin 996 Contact-sorption molybdenums of 200ml/h, take and flow out Mo concentration and reach 0.02g/l as adsorbing terminal.By mass concentration: 2.5%NaOH+5.0%NaCl, 8%H
2O
2Resolve regeneration for resolving agent with the flow velocity of 100ml/h.Vanadium molybdenum degree of depth separating experiment result (g/l) containing vanadium, molybdenum solution is as follows:
| ? | V 2O 5 | Mo | SiO 2 | P | As |
| Original solution | 1.68 | 0.51 | 0.01 | 0.002 | 0.002 |
| Except liquid after molybdenum | 1.67 | 0.01 | 0.01 | 0.001 | 0.001 |
| The molybdenum desorbed solution | 0.01 | 9.13 | 0.00 | 0.001 | 0.001 |
Embodiment 2:
Get 3.5L containing vanadium, molybdenum solution V
2O
5=1.50g/l, Mo=0.41g/l, stir and add sulfuric acid to adjust pH to 1.92, adds Na
2SO
3Fully reaction, pass into air and adjust solution potential to 585mv, and with flow velocity and the 100ml resin 921 Contact-sorption molybdenums of 200ml/h, the outflow Mo concentration of take reaches 0.02g/l as the absorption terminal.2.5%NaOH+5.0%NaCl resolves regeneration for resolving agent with the flow velocity of 100ml/h.Vanadium molybdenum degree of depth separating experiment result (g/l) containing the vanadium sodium molybdate solution is as follows:
| ? | V 2O 5 | Mo | SiO2 | P | As |
| Original solution | 1.50 | 0.41 | 0.01 | 0.002 | 0.002 |
| Except liquid after molybdenum | 1.50 | 0.01 | 0.01 | 0.001 | 0.001 |
| The molybdenum desorbed solution | 0.01 | 8.45 | 0.00 | 0.001 | 0.001 |
Embodiment 3:
Get 3.5L containing vanadium ammonium molybdate solution V
2O
5=1.66g/l, Mo=0.62g/l, stir and add sulfuric acid to adjust pH to 1.96, adds Na
2S fully reacts, and adds H
2O
2Adjust the solution oxide reduction potential to 590mv, with flow velocity and the 100ml resin D296 Contact-sorption molybdenum of 200ml/h, the outflow Mo concentration of take reaches 0.02g/l as the absorption terminal.2.5%NaOH+5.0%NaClO resolves regeneration for resolving agent with the flow velocity of 100ml/h.The vanadium molybdenum degree of depth separating experiment result (g/l) of solution is as follows:
| ? | V 2O 5 | Mo | SiO2 | P | As |
| Original solution | 1.66 | 0.62 | 0.01 | 0.002 | 0.002 |
| Except liquid after molybdenum | 1.65 | 0.01 | 0.01 | 0.001 | 0.001 |
| The molybdenum desorbed solution | 0.02 | 13.06 | 0.00 | 0.001 | 0.001 |
The invention has the advantages that, by changing the vanadium molybdenum, have valence state, the vanadium molybdenum is existed with different hydrated ion forms, by Choice of Resin absorption, separate thereby reach the vanadium molybdenum degree of depth.
Claims (10)
1. a vanadium, molybdenum degree of depth separation method is characterized in that:
1) pH adjustment: first to the solution containing vanadium and molybdenum, add the 92.5%-98% vitriol oil to adjust pH to 1-5;
2) ionic condition adjustment: add respectively reductive agent, oxygenant in solution, adjust the solution oxide reduction potential, thereby vanadium, molybdenum ion are existed with the form of positively charged ion and negatively charged ion respectively;
3) resin ion-exchange separates: above-mentioned solution is continuously by filling the exchange column of strongly basic anion exchange resin, exchange velocity is by 20-30min control duration of contact, the Mo of take in effluent liquid reaches 0.02g/l as absorption terminal, the i.e. breakthrough point of Mo in adsorption process; Obtain the vanadium desorbed solution;
Resolve the resin of load Mo to resolve agent, resolution speed, by 40-60min control duration of contact, is effectively resolved the resin of load molybdenum, resolves molybdenum; Obtain the molybdenum desorbed solution.
2. method according to claim 1 is characterized in that: the concentration of the described Molybdenum in Solution containing vanadium and molybdenum is 0.2-2.0g/l; Solution vanadium concentration is with V
2O
5Count 0-2.0g/l.
3. method according to claim 1 is characterized in that: the ionic condition adjustment, at first control pH value of solution=1-5, and add respectively reductive agent and oxygenant to adjust the redox potential of solution, detect VO
2+And VO
2 +Content, make vanadium with VO
2+The valency form exists, and molybdenum exists with the form of negatively charged ion.
4. according to the described method of claim 1 or 3, it is characterized in that: it is Na that ionic condition is adjusted reductive agent used
2SO
3, Na
2S, H
2S, SO
2In one or two or more kinds.
5. according to the described method of claim 1 or 3, it is characterized in that: it is one or two or more kinds in clorox, sodium chlorate, air, hydrogen peroxide that ionic condition is adjusted oxygenant used.
6. according to the described ionic condition inflation method of claim 1 or 3, it is characterized in that: described redox potential is 300-700mv.
7. method according to claim 1, it is characterized in that: strongly basic anion exchange resin used is one or two or more kinds in D296 or 996,921 extration resins.
8. method according to claim 1, it is characterized in that: described parsing agent is one or two or more kinds mixture in mass concentration 30% industrial sodium hydroxide solution, mass concentration 10% sodium chloride solution, the industrial clorox of mass concentration 10%, the industrial hydrogen peroxide of mass concentration 28%.
9. method according to claim 1 is characterized in that: described resin, after resolving agent and resolving, can be reused.
10. method according to claim 1 is characterized in that:
The vanadium desorbed solution can return to vanadium chemistry product production line, with raw material, jointly leaches, and produces AMV and reclaims;
The molybdenum desorbed solution, through acidity adjustment (pH2-2.5), make precipitate molybdic acid, and the separate solid product reoxidizes roasting (650 ℃) and obtains MoO
3.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294045A (en) * | 2014-11-05 | 2015-01-21 | 中南大学 | Method for deeply removing vanadium from vanadium-bearing tungstate solution |
| JP2016073902A (en) * | 2014-10-03 | 2016-05-12 | 栗田工業株式会社 | Method and apparatus for electric deionization treatment of vanadium-containing water |
| CN105692698A (en) * | 2016-02-24 | 2016-06-22 | 中南大学 | Method for deeply separating molybdenum and vanadium in solution containing molybdenum and vanadium |
| WO2018104803A1 (en) * | 2016-12-08 | 2018-06-14 | Metoxs Pte, Ltd. | Recovery of gold and silver from precious metals-containing solids |
| CN108559843A (en) * | 2018-05-25 | 2018-09-21 | 中国科学院过程工程研究所 | A method of processing bone coal pickle liquor |
| CN108707766A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of separating and recovering uranium and molybdenum from bone coal pickle liquor |
| CN108754191A (en) * | 2018-05-25 | 2018-11-06 | 中国科学院过程工程研究所 | A method of processing bone coal pickle liquor |
| CN110407283A (en) * | 2019-07-25 | 2019-11-05 | 江苏南大环保科技有限公司 | A kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment |
| CN111118310A (en) * | 2020-01-15 | 2020-05-08 | 燕山大学 | Method for extracting and separating vanadium and molybdenum in aqueous solution |
Citations (3)
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| US4051221A (en) * | 1975-04-16 | 1977-09-27 | Akzona Incorporated | Process for the separate recovery of vanadium and molybdenum |
| CN101062785A (en) * | 2006-04-26 | 2007-10-31 | 中南大学 | Method for deeply removing vanadium of vanadium-containing molybdate solution |
| CN102876895A (en) * | 2012-10-09 | 2013-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium and chromium from low-concentration pentavalent vanadium and hexavalent chromium mixed liquor |
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2013
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Patent Citations (3)
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| CN102876895A (en) * | 2012-10-09 | 2013-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium and chromium from low-concentration pentavalent vanadium and hexavalent chromium mixed liquor |
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| 曾理等: "离子交换法从钼酸铵溶液中分离钼钒的研究", 《稀有金属与硬质合金》, vol. 34, no. 2, 30 June 2006 (2006-06-30) * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016073902A (en) * | 2014-10-03 | 2016-05-12 | 栗田工業株式会社 | Method and apparatus for electric deionization treatment of vanadium-containing water |
| CN104294045A (en) * | 2014-11-05 | 2015-01-21 | 中南大学 | Method for deeply removing vanadium from vanadium-bearing tungstate solution |
| CN105692698A (en) * | 2016-02-24 | 2016-06-22 | 中南大学 | Method for deeply separating molybdenum and vanadium in solution containing molybdenum and vanadium |
| CN105692698B (en) * | 2016-02-24 | 2017-06-09 | 中南大学 | The depth separation method of molybdenum, vanadium in a kind of vanadium solution containing molybdenum |
| WO2018104803A1 (en) * | 2016-12-08 | 2018-06-14 | Metoxs Pte, Ltd. | Recovery of gold and silver from precious metals-containing solids |
| US11434576B2 (en) | 2016-12-08 | 2022-09-06 | Clean Resources Pte. Ltd | Recovery of gold and silver from precious metals-containing solids |
| CN108707766A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of separating and recovering uranium and molybdenum from bone coal pickle liquor |
| CN108754191A (en) * | 2018-05-25 | 2018-11-06 | 中国科学院过程工程研究所 | A method of processing bone coal pickle liquor |
| CN108707766B (en) * | 2018-05-25 | 2020-12-29 | 中国科学院过程工程研究所 | Method for separating and recycling uranium and molybdenum from stone coal pickle liquor |
| CN108559843A (en) * | 2018-05-25 | 2018-09-21 | 中国科学院过程工程研究所 | A method of processing bone coal pickle liquor |
| CN110407283A (en) * | 2019-07-25 | 2019-11-05 | 江苏南大环保科技有限公司 | A kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment |
| CN110407283B (en) * | 2019-07-25 | 2022-04-22 | 江苏南大环保科技有限公司 | Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater |
| CN111118310A (en) * | 2020-01-15 | 2020-05-08 | 燕山大学 | Method for extracting and separating vanadium and molybdenum in aqueous solution |
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Application publication date: 20131204 |