CN102925686B - Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium - Google Patents
Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium Download PDFInfo
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Abstract
The invention discloses a method for selectively separating and extracting vanadium and chromium from a solution containing the vanadium and the chromium. The method comprises the following steps: (1) NaHSO3 is added to reduce V (V) and Cr (VI) into V (IV) and Cr (III), (2) H2O2 is added to oxidize the V (IV) into V (V), (3) an ion exchange column is used to selectively absorb anions containing the vanadium, and effluent before penetrating is collected, (4) the chromium in the ion exchange column is washed down, and the effluent before penetrating is added to extract the chromium, (5) NaOH is used to elute resin carrying the vanadium to obtain eluant containing the vanadium, (6) ammonium metavanadate is prepared from the eluant and then roasted to obtain V2O5, and (7) the potential of hydrogen (PH)of a chromium solution is adjusted to enable the chromium to be separated out in the form of Cr(OH)3.nH2O, and then Cr2O3 powder is obtained through roasting. The method for selectively separating and extracting the vanadium and the chromium from the solution containing the vanadium and the chromium achieves efficient separation and high-purity extraction of the vanadium and the chromium, the overall recovery rate respectively reaches 82-90 % and 94-99 %, the purity of finished products respectively reaches 96-99 % and 94-97 %.
Description
Technical field
The present invention relates to a kind of method of effective extraction vanadium, chromium, be specifically related to a kind of from the solution containing vanadium, chromium selective separation and extract the method for vanadium, chromium, belong to the hydrometallurgy field of vanadium.
Background technology
In modernization industry technology, vanadium and chromium are important valuable metal elements, are all widely used in metallurgical industry and chemical industry.In existing blast-furnace smelting-bessemerize-vanadium slag sodium roasting-water logging vanadium extraction operation taking vanadium titano-magnetite as raw material, because chromium is similar to the character of vanadium, vanadium, chromium in vanadium titano-magnetite are all reduced into molten iron in blast-furnace smelting, in converter oxidation is smelted, chromium enters in vanadium slag with vanadium is oxidized.In the Roasting And Leaching process in later stage, part chromium is leached with vanadium, forms the mixing solutions containing vanadium, chromium.Chromium is mixed in containing affecting the precipitation rate of precipitation process and the purity of vanadium product in vanadium leachate.In addition, large containing the solution toxicity of high valence state vanadium and chromium, serious harm environment.Therefore, effective selectivity separation and recovery vanadium and chromium are the keys of vanadium hydrometallurgy process.
Process containing the method for vanadium, chromium solution and have solvent extraction and separation method, ion-exchange adsorption method of separation and selective precipitation partition method at present.Thereby the patent research that publication number is CN1121962A make extraction agent with primary amine varies and realize with selective extraction vanadium the method that vanadium, chromium separate to carry out reverse-flow contact containing vanadium, chromium solution, the method arrives water with alkali lye by vanadium back extraction, solution containing vanadium is pressed the vanadium extraction of ammonium salt precipitation method, and raffinate is carried chromium by reduction-neutralisation.The shortcoming of the method is, the finite capacity of extraction agent be difficult to obtain the vanadium of high density, and treatment process is tediously long, complicated operation.Publication number be CN102337411 patent research spent ion exchange resin from the low vanadium vanadium wastewater of high chromium, reclaim the method for vanadium and chromium.The vanadium of high valence state by resin absorption wash-out, is realized vanadium in elutriant, chromium separation by ammonium salt precipitation method together with chromium, and after precipitation, solution extracts chromium by the reduction-neutralization-precipitator method.The method is extracted vanadium and chromium with ion-exchange-resin process purification-precipitation separation, and shortcoming is can not realize the high separation of vanadium, chromium and obtain high purity vanadium and chromium goods, and complicated operation.Contain vanadium, chromium waste liquid for the secondary extracting after vanadium, chromium, vanadium chromium slag is obtained in its reduction precipitation by industrial conventional reductive agent, vanadium chromium slag is again through roasting, with selective oxidation, selectivity leaches to realize vanadium then, chromium separates, the shortcoming of the method be vanadium chromium slag subsequent disposal amount large, and selectivity while leaching required sulfuric acid consumption very large, make the cost of the method high, and environmental pollution is serious.
Summary of the invention
For prior art above shortcomings, the object of this invention is to provide a kind of cost lower, operate better simply from the method containing effectively separating and extract vanadium and chromium vanadium, chromium solution, the method can obtain highly purified vanadium and chromium goods, has realized high efficiente callback utilization and the environmental friendliness of resource.
Technical scheme of the present invention is achieved in that
A method for selective separation and extraction vanadium and chromium from the solution containing vanadium, chromium, it comprises the following steps,
(1) regulate pending vanadium, chromium solution pH to 1.5 ~ 4.5 of containing, add the NaHSO of 0.6 ~ 0.8 times according to the volumetric molar concentration sum of (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) by stoichiometric number
3, heated and stirred 3 ~ 4h at 55 ~ 65 DEG C, makes to be reduced to respectively V (IV) and Cr (III) containing the V (V) in vanadium, chromium solution and Cr (VI);
(2) regulating the pH value of (1) step gained solution is 3.0 ~ 5.5, then presses H
2o
2/ V mol ratio is that 20 ~ 30 ratio adds 30wt%H
2o
2, at 35 ~ 45 DEG C, stir 6 ~ 8h, optionally V (IV) is oxidized to V (V), then at 90 ~ 99 DEG C, heating makes H
2o
2decompose, until solution no longer produces bubble, and check constant indigo plant with starch potassium iodide paper;
(3) (2) step gained pH value of solution is adjusted to 2.5 ~ 5.5, adds in the exchange column with macroporous weakly basic anion exchange resin dress post,, containing vanadium negatively charged ion the effluent liquid before running through is collected with for subsequent use by this exchange column selective adsorption;
(4) with the washing composition of 0.8 ~ 4.0 times of resin volume, the chromium remaining in ion exchange column is washed, and add the effluent liquid before running through to form chromium solution to carry chromium the washings obtaining;
(5) by 2 ~ 5%NaOH(mass concentration of 3 ~ 8 times of resin volumes) resin of eluant solution load vanadium, obtain the elutriant containing vanadium;
The elutriant of (6) (5) steps adopts the alkaline ammonium salt precipitator method to make ammonium meta-vanadate, and then at 550 ~ 600 DEG C, calcining obtains V
2o
5product;
(7) chromium solution pH to 8.0 ~ 8.8 of adjusting (4) step gained, chromium is with hydrate deposition Cr (OH)
3nH
2the form of O is separated out, and at 1000～1150 DEG C, calcining (time 3h) obtains Cr
2o
3powder.
When (3) step exchange column selective adsorption contains vanadium negatively charged ion, to contain vanadium concentration in effluent liquid as 1.3mmol/L is as penetration.
The washing composition of the selected residual chromium of (4) step is unsaturated carbonate solution.
The present invention is used for regulating the bronsted lowry acids and bases bronsted lowry of pH to be respectively H
2sO
4and NaOH.
Present device requires simple, and process costs is low, can realize high efficiency separation and the high purity thereof of vanadium and chromium and extract.With present method recovery vanadium and chromium, total yield can reach respectively 82 ~ 90% and 94% ~ 99%, and finished product purity can reach respectively 96 ~ 99% and 94 ~ 97%.Resin is reused after 3% ~ 5%HCl solution makes the transition.
Embodiment
The present invention is from the method containing selective separation vanadium, chromium solution and extraction vanadium and chromium, and it comprises the following steps,
(1) regulate pending vanadium, chromium solution pH to 1.5 ~ 4.5 of containing, add the NaHSO of 0.6 ~ 0.8 times according to the volumetric molar concentration sum of (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) by stoichiometric number
3, heated and stirred 3 ~ 4h at 55 ~ 65 DEG C, makes to be reduced to respectively V (IV) and Cr (III) containing the V (V) in vanadium, chromium solution and Cr (VI); Chemical equation is expressed as follows:
(2) regulating the pH value of (1) step gained solution is 3.0 ~ 5.5, then presses H
2o
2/ V mol ratio is that 20 ~ 30 ratio adds 30wt%H
2o
2, at 35 ~ 45 DEG C, stir 6 ~ 8h, optionally V (IV) is oxidized to V (V), then at 90 ~ 99 DEG C, heating makes H
2o
2decompose, until solution no longer produces bubble, and check constant indigo plant with starch potassium iodide paper.V (V) and H
2o
2main in conjunction with forming vanadium peroxide root complicated ions under solutions of weak acidity
, Cr (III) is with Cr
3+form exist.At 90～99 DEG C, heat 2 ~ 4h, vanadium with
form is present in solution.Chemical equation is expressed as follows:
(3) (2) step gained pH value of solution is adjusted to 2.5 ~ 5.5, add in the ion exchange column with macroporous weakly basic anion exchange resin dress post, to realize resin as 1.3mmol/L as penetration to containing the absorption of vanadium negatively charged ion containing vanadium concentration in effluent liquid, vanadium with
form is adsorbed by this Choice of Resin, Cr
3+be not adsorbed, remain in effluent liquid, the effluent liquid before running through is collected with for subsequent use;
(4) remain in the chromium in ion exchange column with the unsaturated carbonate solution washing of 0.8 ~ 4.0 times of resin volume, and add the effluent liquid before running through to form chromium solution to carry chromium washings;
(5) by 2 ~ 5%NaOH(mass concentration of 3 ~ 8 times of resin volumes) the negative vanadium resin of eluant solution, obtain the elutriant containing vanadium, resin is reused after 3% ~ 5% HCl solution transition;
By the separation of above-mentioned steps (3)-(5), vanadium recovery is 90 ~ 95% left and right, and chromium recovery ratio is greater than 99%; Content≤0.03% of chromium in elutriant, separates content of vanadium≤0.01% in the chromium-containing solution after vanadium, has realized the high efficiency separation of vanadium and chromium.
The elutriant of (6) (5) step gained adopts the alkaline ammonium salt precipitator method to make ammonium meta-vanadate, and then at 550 ~ 600 DEG C, calcining obtains V
2o
5product;
(7) chromium solution pH to 8.0 ~ 8.8 of adjusting (4) step gained, chromium is with hydrate deposition Cr (OH)
3nH
2the form of O is separated out, and calcines 3h and obtain Cr at 1000～1150 DEG C
2o
3powder.
The present invention is used for regulating the bronsted lowry acids and bases bronsted lowry of pH value to be respectively H
2sO
4and NaOH.
Below in conjunction with concrete example, the present invention is described in detail.
Example 1
1.5L is containing the vanadium slag leach liquor of vanadium (83mmol/L) and chromium (57mmol/L), and after Tai-Ace S 150 removal of impurities, at 50 DEG C, 0.6 times that pH is the volumetric molar concentration sum according to (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) adds 24g NaHSO
3, at 65 DEG C, heated and stirred 3h is with vanadium and chromium in reduction mixing solutions.Then press H
2o
2/ V mol ratio is 25 to add 30wt% H
2o
2volume is 240ml, then at 99 DEG C, is heated to no longer produce bubble, checks constant indigo plant with starch potassium iodide paper.Now, vanadium is present in solution with anion radical form, and chromium is with Cr
3+form exists.
The pH value of solution that will contain high price vanadium low price chromium be adjusted to 3.3, and in exchange column, the selective adsorption of macroreticular weakly base Chioro-anion exchange resin is containing vanadium anion radical, and to contain vanadium concentration in effluent liquid as 1.3mmol/L is as penetration, the effluent liquid before running through is collected with for subsequent use.Remain in the chromium in exchange column with the carbonation solution washing of 2 times of resin volumes, and add effluent liquid before running through to carry chromium washings.Carry vanadium resin with 3% NaOH eluant solution of 5 times of resin volumes, elutriant is collected vanadium extraction for subsequent use.
Regulate elutriant pH to 8.8, obtain ammonium meta-vanadate precipitation, obtain V 550 DEG C of these precipitations of calcining
2o
5powder.Adjusting runs through front effluent liquid and the washings pH to 8.2 containing chromium, and chromium is with hydrate deposition Cr (OH)
3the form of nH2O is separated out, and calcines 3h and obtain Cr at 1000 DEG C
2o
3powder.The total yield that obtains vanadium and chromium is respectively 90.2% and 98.3%, and finished product purity is respectively 98.6% and 96.3%.
Example 2
1.5L is containing the vanadium slag leach liquor of vanadium (83mmol/L) and chromium (57mmol/L), and after Tai-Ace S 150 removal of impurities, at 40 DEG C, 0.7 times that pH is the volumetric molar concentration sum according to (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) adds 28g NaHSO
3, at 65 DEG C, heated and stirred 3h is with vanadium and chromium in reduction mixing solutions.Then press H
2o
2/ V mol ratio is 30 to add 30wt% H
2o
2volume is 290ml, then at 99 DEG C, is heated to no longer produce bubble, checks constant indigo plant with starch potassium iodide paper.Now, vanadium is present in solution with anion radical form, and chromium is with Cr
3+form exists.
The pH value of solution that will contain high price vanadium low price chromium be adjusted to 3.0, and in exchange column, the selective adsorption of macroreticular weakly base Chioro-anion exchange resin is containing vanadium anion radical, and to contain vanadium concentration in effluent liquid as 1.3mmol/L is as penetration, the effluent liquid before running through is collected with for subsequent use.Remain in the chromium in exchange column with the carbonation solution washing of 3 times of resin volumes, and add effluent liquid before running through to carry chromium washings.Carry vanadium resin with 5% NaOH eluant solution of 6 times of resin volumes, elutriant is collected vanadium extraction for subsequent use.
Regulate elutriant pH to 8.8, obtain ammonium meta-vanadate precipitation, obtain V 550 DEG C of these precipitations of calcining
2o
5powder.Adjusting runs through front effluent liquid and the washings pH to 8.2 containing chromium, and chromium is with hydrate deposition Cr (OH)
3the form of nH2O is separated out, and calcines 3h and obtain Cr at 1000 DEG C
2o
3powder.The total yield that obtains vanadium and chromium is respectively 86.5% and 96.7%, and finished product purity is respectively 96.7% and 95.1%.
Example 3
1.5L is containing the vanadium slag leach liquor of vanadium (83mmol/L) and chromium (57mmol/L), and after Tai-Ace S 150 removal of impurities, at 60 DEG C, 0.8 times that pH is the volumetric molar concentration sum according to (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) adds 32g NaHSO
3, at 65 DEG C, heated and stirred 3h is with vanadium and chromium in reduction mixing solutions.Then press H
2o
2/ V mol ratio is 25 to add 30wt% H
2o
2volume is 240ml, then at 99 DEG C, is heated to no longer produce bubble, checks constant indigo plant with starch potassium iodide paper.Now, vanadium is present in solution with anion radical form, and chromium is with Cr
3+form exists.
The pH value of solution that will contain high price vanadium low price chromium be adjusted to 3.8, and in exchange column, the selective adsorption of macroreticular weakly base Chioro-anion exchange resin is containing vanadium anion radical, and to contain vanadium concentration in effluent liquid as 1.3mmol/L is as penetration, the effluent liquid before running through is collected with for subsequent use.Remain in the chromium in exchange column with the carbonation solution washing of 4 times of resin volumes, and add effluent liquid before running through to carry chromium washings.Carry vanadium resin with 3% NaOH eluant solution of 5 times of resin volumes, elutriant is collected vanadium extraction for subsequent use.
Regulate elutriant pH to 8.8, obtain ammonium meta-vanadate precipitation, obtain V 550 DEG C of these precipitations of calcining
2o
5powder.Adjusting runs through front effluent liquid and the washings pH to 8.2 containing chromium, and chromium is with hydrate deposition Cr (OH)
3the form of nH2O is separated out, and calcines 3h and obtain Cr at 1000 DEG C
2o
3powder.The total yield that obtains vanadium and chromium is respectively 83.3% and 95.5%, and finished product purity is respectively 97.6% and 94.4%.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (2)
1. a method for selective separation and extraction vanadium and chromium from the solution containing vanadium, chromium, is characterized in that: it comprises the following steps:
(1) regulate pending vanadium, chromium solution pH to 1.5～4.5 of containing, add the NaHSO of 0.6～0.8 times according to the volumetric molar concentration sum of (V) volumetric molar concentration of V in waste liquid and 3 times of Cr (VI) by stoichiometric number
3, heated and stirred 3～4h at 55～65 DEG C, makes to be reduced to respectively V (IV) and Cr (III) containing the V (V) in vanadium, chromium solution and Cr (VI);
Cr
2O
7 2-+3HSO
3 -+5H
+→2Cr
3++3SO
4 2-+4H
2O(1.6≤pH≤1.9)
2VO
2 ++HSO
3 -+H
+→2VO
2++SO
4 2-+H
2O(1.6≤pH≤1.9)
(2) regulating the pH value of (1) step gained solution is 3.0～5.5, and presses H
2o
2/ V mol ratio is that 20～30 ratio adds 30wt%H
2o
2, at 35～45 DEG C, stir 6～8h, optionally V (IV) is oxidized to V (V), then at 90～99 DEG C, heating makes H
2o
2decompose, until solution no longer produces bubble, and check constant indigo plant with starch potassium iodide paper;
2VO
2++5H
2O
2→2VO
2(O
2)
2 3-+10H
+
(3) (2) step gained pH value of solution is adjusted to 2.5～5.5, adds in the ion exchange column with macroreticular weakly base Chioro-anion exchange resin dress post and contain vanadium negatively charged ion with selective adsorption, the effluent liquid before running through is collected with for subsequent use;
H
2V
10O
28 4- (l)+4R-Cl
(s)→R
4-H
2V
10O
28(s)+4Cl
- (l)(pH=3.0)
(4) with the washing composition of 0.8～4.0 times of resin volume, the chromium remaining in ion exchange column is washed, and add the effluent liquid before running through to form chromium solution to carry chromium the washings obtaining;
In described washing column, the washing composition of residual chromium is unsaturated carbonate solution;
(5) resin of the NaOH eluant solution load vanadium that is 2～5% by the mass concentration of 3～8 times of resin volumes, obtains the elutriant containing vanadium;
The elutriant of (6) (5) steps adopts the alkaline ammonium salt precipitator method to make ammonium meta-vanadate, and then at 550～600 DEG C, calcining obtains V
2o
5product;
(7) chromium solution pH to 8.0～8.8 of adjusting (4) step gained, chromium is with hydrate deposition Cr (OH)
3nH
2the form of O is separated out, and at 1000～1150 DEG C, calcining obtains Cr
2o
3powder.
According to claim 1 from the solution containing vanadium, chromium selective separation and extract the method for vanadium and chromium, it is characterized in that: make spent ion exchange resin in the time of exchange column internal adsorption vanadium, to contain vanadium concentration in effluent liquid as 1.3mmol/L is as penetration.
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|---|---|---|---|
| CN201210455895.9A CN102925686B (en) | 2012-11-14 | 2012-11-14 | Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium |
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| CN201210455895.9A CN102925686B (en) | 2012-11-14 | 2012-11-14 | Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium |
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| CN102925686B true CN102925686B (en) | 2014-06-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276205B (en) * | 2013-05-29 | 2014-12-10 | 东北大学 | Method for separating and extracting vanadium and chromium from vanadium chromium leaching liquor |
| CN103602819B (en) * | 2013-11-29 | 2015-02-11 | 中南大学 | Comprehensive recovery method of vanadate-chromate-containing solution |
| CN107190155A (en) * | 2017-05-19 | 2017-09-22 | 重庆大学 | Vanadium, the method for chromium are extracted in a kind of mixed liquor from containing vanadium and chromium |
| CN110642414B (en) * | 2019-01-30 | 2022-04-15 | 江苏南大环保科技有限公司 | Control method for efficiently separating vanadium-chromium wastewater by using modified chelate resin |
| CN110642413B (en) * | 2019-01-30 | 2022-04-22 | 江苏南大环保科技有限公司 | Treatment method for coupling vanadium-chromium wastewater strengthening pretreatment and modified chelate resin |
| 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 |
| CN111057876B (en) * | 2019-11-30 | 2021-09-21 | 重庆大学 | Method for preparing high-purity vanadium pentoxide by microemulsion extraction |
| CN111057875B (en) * | 2019-11-30 | 2021-09-21 | 重庆大学 | Method for separating vanadium and chromium from solution by using microemulsion |
| CN115404361B (en) * | 2022-09-02 | 2023-09-29 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadyl sulfate solution from industrial vanadium slag sodium roasting water leaching solution |
| CN116334414A (en) * | 2023-03-16 | 2023-06-27 | 核工业北京化工冶金研究院 | Method for selectively separating vanadium and chromium from vanadium-chromium solution |
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| CN101538652B (en) * | 2009-04-14 | 2011-01-12 | 杨秋良 | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste |
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