CN109023410B - Method for separating and extracting vanadium from vanadium-containing solution - Google Patents
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- CN109023410B CN109023410B CN201811029539.4A CN201811029539A CN109023410B CN 109023410 B CN109023410 B CN 109023410B CN 201811029539 A CN201811029539 A CN 201811029539A CN 109023410 B CN109023410 B CN 109023410B
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Abstract
The invention provides a method for separating and extracting vanadium from a vanadium-containing solution, which comprises the following steps: step 1, adding sulfuric acid into vanadium-containing solution, and adjustingThe ratio of vanadium to total sulfur, namely, electrolyzing and reducing vanadium in the vanadium-containing solution to trivalent by using an electrolytic cell to obtain a vanadium sulfate-containing solution; step 2, adding concentrated sulfuric acid into the solution containing vanadium sulfate to improve the ratio of sulfur to vanadium; step 3, cooling, stirring and reacting for a period of time, and filtering to obtain vanadium sulfate V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor containing impurities, wherein x is more than or equal to 1 and more than or equal to 0. The method for separating and extracting vanadium from the vanadium-containing solution can deeply separate vanadium and impurities in the vanadium-containing solution to obtain vanadium sulfate crystals, and is simple and easy to implement and low in separation cost.
Description
Technical Field
The invention relates to a hydrometallurgy technology, in particular to a method for separating and extracting vanadium from a vanadium-containing solution.
Background
At present, more methods for extracting vanadium compounds from vanadium-containing solutions are available, including: red vanadium precipitation, ammonium salt precipitation, iron salt precipitation and calcium salt precipitation. Among them, the vanadium-molybdenum separation effect of the red vanadium precipitation method and the ammonium salt precipitation method is not good, and the vanadium-potassium separation effect has a certain problem. The iron salt precipitation method and the calcium salt precipitation method are more suitable for treating low-concentration vanadium solution, such as vanadium-containing wastewater (the vanadium content is more than or equal to 20g/L), and the obtained product has poor purity, so that the application of the product is limited.
The electrolyte of the all-vanadium redox flow battery is a sulfate solution rich in vanadium with mixed valence, the traditional method for extracting vanadium is to firstly precipitate ammonium vanadate, calcine the ammonium vanadate to obtain vanadium oxide, and obtain an electrolyte solution through acid dissolution or electrolysis, the process is long, the production operation is responsible, the cost is high, a large amount of ammonium-containing wastewater is generated, the treatment cost is high, and the cost is higher and higher under the condition that the environmental protection supervision is more and more strict. The method for extracting vanadium from the vanadium-containing solution with good separation effect and low separation cost is urgently needed.
Disclosure of Invention
The invention aims to provide a method for separating and extracting vanadium from a vanadium-containing solution, aiming at the problems of poor separation effect and high separation cost of methods for extracting vanadium compounds from the vanadium-containing solution in different degrees.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for separating and extracting vanadium from a vanadium-containing solution comprises the following steps:
step 1, adding sulfuric acid into a vanadium-containing solution, adjusting the ratio of sulfur to vanadium, and electrolytically reducing vanadium in the vanadium-containing solution to trivalent by using an electrolytic cell to obtain a vanadium sulfate-containing solution;
step 2, adding concentrated sulfuric acid into the solution containing vanadium sulfate to improve the ratio of sulfur to vanadium;
step 3, cooling, stirring and reacting for a period of time, and filtering to obtain vanadium sulfate V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor containing impurities, wherein x is more than or equal to 1 and more than or equal to 0.
Further, in the step 1, the vanadium-containing solution is prepared by dissolving vanadium-containing raw materials in water. The vanadium-containing raw material includes but is not limited to V-containing2O5Petroleum ash, industrial ammonium metavanadate, industrial V2O5One or more of industrial ammonium polyvanadate, vanadium-containing steel slag and vanadium slag. The V is2O5The petroleum burning ash is dissolved in water after sodium roasting, and vanadium-containing solution (sodium vanadate solution) is prepared. The industrial ammonium metavanadate is dissolved into vanadium-containing solution by adding sodium hydroxide and water. The said industry V2O5Adding sodium hydroxide and water to dissolve into vanadium-containing solution.
Further, the concentration of vanadium ions in the vanadium-containing solution in the step 1 is 0.1-5mol/L, preferably 1-3 mol/L.
Further, the amount ratio of sulfur to vanadium in step 1 is S: V.gtoreq.1.5, preferably 5. gtoreq.S: V.gtoreq.1.5.
Further, the electrolysis parameter in the step 1 is that the current density is 50-150A/m2Electrolyzing at 0-50 deg.C for 2-10h, preferably at current density of 70-100A/m2Electrolyzing at 10-50 deg.C for 4-6h, preferably at 80A/m2Electrolyzing for 5h at room temperature.
Further, the concentration of sulfuric acid in step 1 is 50-92.5% wt.
Further, the concentration of the concentrated sulfuric acid in the step 2 is 92.5-99.8% wt.
Further, the amount ratio of sulfur and vanadium in step 2 is in the range of 10. gtoreq.S: V > 1.5, preferably 6. gtoreq.S: V > 3.
Further, the cooling temperature in step 3 is 0 to 60 ℃, preferably 10 to 30 ℃.
Further, the reaction time in step 3 is 0.1 to 48 hours, preferably 4 to 12 hours.
According to the method for separating and extracting vanadium from the vanadium-containing solution, the separation of vanadium and impurities in the vanadium-containing solution is realized through dissolution and crystallization, the vanadium sulfate solid is obtained, and the vanadium sulfate solid is dissolved by water to obtain the all-vanadium redox flow battery electrolyte. Compared with the prior art, the method for separating and extracting vanadium from the vanadium-containing solution has the following advantages:
1) the method comprises the steps of reducing vanadium in a vanadium-containing solution into trivalent vanadium sulfate solution through electrolytic reduction to form a vanadium sulfate solution, adding sulfuric acid to promote the supersaturation of the vanadium sulfate, crystallizing and precipitating in the form of sulfuric acid and vanadium sulfate double salt to obtain crystals, and realizing the separation of vanadium from the solution and impurities;
2) the method can deeply separate vanadium and impurities in the vanadium-containing solution to obtain vanadium sulfate crystals, and the process avoids using ammonium salt, thereby reducing the discharge of three wastes and energy consumption and simultaneously reducing the production cost;
3) the vanadium sulfate crystal prepared by the method has high purity, and can be directly used for preparing the electrolyte of the all-vanadium redox flow battery;
4) the method for separating and extracting vanadium from the vanadium-containing solution is simple and easy to implement, has low separation cost, and can be widely applied to V-containing solution2O5Petroleum ash, industrial ammonium metavanadate, industrial V2O5And recovering vanadium from vanadium-containing raw materials such as industrial ammonium polyvanadate, vanadium-containing steel slag, vanadium slag and the like.
Drawings
FIG. 1 is an XRD picture of vanadium sulfate crystals obtained in example 1;
FIG. 2 is a scanning electron micrograph (1000 times) of the vanadium sulfate crystal obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The implementation discloses a method for separating and extracting vanadium from a vanadium-containing solution, taking separation of vanadium in industrial ammonium metavanadate as an example (the content of molybdenum in the industrial ammonium metavanadate is 1.2 wt%, and V is used as2O5The gauge concentration was 73.5% wt). The method for separating and extracting vanadium from vanadium-containing solution comprises the following steps：
Step 1, adding sodium hydroxide and water to industrial ammonium metavanadate to dissolve the industrial ammonium metavanadate into vanadium-containing solution, adding sodium hydroxide to completely dissolve the ammonium metavanadate, wherein V is used in the vanadium-containing solution2O5Measuring the concentration to be 188g/L, and taking 1L vanadium-containing solution;
step 2, adding 240ml of 92.5 percent wt sulfuric acid into the vanadium-containing solution at room temperature, and uniformly stirring;
and 3, putting the vanadium-containing solution obtained in the step 2 into an electrolytic cell, and carrying out electrolytic reduction by using the electrolytic cell under the following electrolytic conditions:
the anolyte is 5% wt sulfuric acid aqueous solution, and the electrode area is 100cm2Electrolyzing at normal temperature and constant current with the current of 1A to obtain a solution containing vanadium sulfate as V2O5The measured concentration is 151 g/L;
step 4, adding 150ml of concentrated sulfuric acid (99.8 percent wt) into the vanadium-containing solution obtained by electrolysis in the step 3, uniformly stirring, adding 2g of vanadium sulfate crystal serving as a seed crystal, cooling to room temperature, stirring for 36 hours, and filtering to obtain vanadium sulfate crystal V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor.
As can be seen from fig. 1 and table 1, the obtained material is vanadium sulfate, the impurity content of the product is low, and meets the requirements of the all-vanadium flow battery electrolyte, and x is 0.069, and n is 9.8, which can be calculated from table 1. FIG. 2 is a scanning electron micrograph of the vanadium sulfate crystal of this example.
TABLE 1 elemental content measurement results (in% by weight) of the vanadium sulfate crystals obtained in example 1
| V | 17.80％ |
| SO4 2 | 52.47％ |
| K | 0.0009％ |
| Na | 0.0005％ |
| Fe | 0.0009％ |
| Al | 0.0007％ |
| Mo | 0.0004％ |
| Cr | 0.0003％ |
| Mn | 0.0000％ |
| Ca | 0.0011％ |
| W | 0.0003％ |
| Mg | 0.0004％ |
Example 2
The implementation discloses a method for separating and extracting vanadium from a vanadium-containing solution, taking the separation of vanadium in petroleum fuel ash as an example, the method comprises the following steps:
step 1, with V2O550 wt% of petroleum fuel ash is subjected to sodium roasting to obtain V2O5The meter comprisesThe amount of the sodium vanadate is changed to 35 percent by weight, and the sodium vanadate solution is obtained by adding water to dissolve the sodium vanadate solution and taking the sodium vanadate solution as V2O5Measuring the concentration to 281g/L, and taking 1L vanadium-containing solution;
step 2, adding 525ml of 92.5 percent wt sulfuric acid into the vanadium-containing solution at room temperature, and uniformly stirring;
and 3, putting the vanadium-containing solution obtained in the step 2 into an electrolytic cell, and carrying out electrolytic reduction by using the electrolytic cell under the following electrolytic conditions:
the anolyte is 5% wt sulfuric acid aqueous solution, and the electrode area is 100cm2Carrying out constant current electrolysis at normal temperature under the condition of current 1A to obtain a solution containing vanadium sulfate with the concentration of 1A;
step 4, adding 200ml of concentrated sulfuric acid (99.8 percent by weight) into the vanadium-containing solution obtained by electrolysis in the step 3, uniformly stirring, adding 2g of vanadium sulfate crystal serving as a seed crystal, cooling to room temperature, stirring for 24 hours, and filtering to obtain vanadium sulfate crystal V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor.
As can be seen from Table 2, the obtained vanadium sulfate has low impurity content and meets the requirements of the electrolyte of the all-vanadium flow battery. From table 2, x is 1 and n is 11.
TABLE 2 elemental content measurement results (unit% wt) of the vanadium sulfate crystals obtained in example 2
Example 3
The implementation discloses a method for separating and extracting vanadium from vanadium-containing solution so as to separate industrial V2O5(potassium content 2.1% wt, as V)2O598.3 wt%) vanadium, comprising the following steps:
step 1, to industry V2O5Dissolving sodium hydroxide solid in water to obtain solution containing V2O5Taking 1L vanadium-containing solution with the concentration of 450 g/L;
step 2, adding 565ml of 92.5 percent wt sulfuric acid into the vanadium-containing solution at room temperature, and uniformly stirring;
and 3, putting the vanadium-containing solution obtained in the step 2 into an electrolytic cell, and carrying out electrolytic reduction by using the electrolytic cell under the following electrolytic conditions:
the anolyte is 5% wt sulfuric acid aqueous solution, and the electrode area is 100cm2Electrolyzing at normal temperature and constant current with the current of 1A to obtain a solution containing vanadium sulfate, already V2O5The measured concentration is 314 g/L;
step 4, adding 175ml of concentrated sulfuric acid (99.8 percent wt) into the vanadium-containing solution obtained by electrolysis in the step 3, uniformly stirring, adding 2g of vanadium sulfate crystal as a seed crystal, cooling to room temperature, stirring for 36 hours, and filtering to obtain vanadium sulfate crystal V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor.
As can be seen from table 3, the obtained vanadium sulfate has a low impurity content, meets the requirements of the all-vanadium flow battery electrolyte, and x is 0.394 and n is 10.5.
TABLE 3 elemental content measurement results (unit% wt) of the vanadium sulfate crystals obtained in example 3
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A method for separating and extracting vanadium from a vanadium-containing solution is characterized by comprising the following steps:
step 1, adding sulfuric acid into a vanadium-containing solution, adjusting the ratio of sulfur to vanadium, and electrolytically reducing vanadium in the vanadium-containing solution to trivalent by using an electrolytic cell to obtain a vanadium sulfate-containing solution; in the step 1, the concentration of the vanadium-containing solution is 0.1-5 mol/L; the mass ratio of sulfur to vanadium is 5 to V is 1.5; the electrolysis parameter is current density of 50-150A/m2Electrolyzing for 2-10h at 0-50 ℃; the vanadium-containing raw material is V-containing2O5Petroleum ash, industrial ammonium metavanadate, industrial V2O5One or more of industrial ammonium polyvanadate, vanadium-containing steel slag and vanadium slag;
step 2, adding concentrated sulfuric acid into the solution containing vanadium sulfate to improve the ratio of sulfur to vanadium, wherein the range of the ratio of the amount of sulfur to the amount of vanadium in the step 2 is more than or equal to 6, and V is more than 3;
step 3, after cooling, stirring and reacting for a period of time, wherein the reaction time is 0.1-48 h; filtering to obtain vanadium sulfate V2(SO4)3`(x)H2SO4.nH2O and crystallization mother liquor containing impurities, wherein x is more than or equal to 1 and more than or equal to 0; the cooling temperature is 0-60 ℃.
2. The method for separating and extracting vanadium from vanadium-containing solution according to claim 1, wherein the concentration of sulfuric acid in step 1 is 50-92.5% wt.
3. The method for separating and extracting vanadium from vanadium-containing solution according to claim 1, wherein the concentrated sulfuric acid concentration in the step 2 is 92.5-99.8 wt%.
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Address after: No.20, Yingchun street, Huayuankou Economic Zone, Dalian, Liaoning, 116450 Patentee after: Dalian Rongke Energy Storage Group Co.,Ltd. Address before: No.20, Yingchun street, Huayuankou Economic Zone, Dalian, Liaoning, 116450 Patentee before: DALIAN BOLONG NEW MATERIALS Co.,Ltd. |