Method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid

Abstract

The invention discloses a method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid, which comprises the following steps: (1) adding hydrochloric acid or sulfuric acid solution into the high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH value to 0.8-1.4, stirring and reacting for 30-180 minutes at 60-90 DEG C, and carrying out solid-liquid separation to obtain precipitate A and vanadium precipitation supernatant; (2) carrying out an oxidation reaction on the precipitate A at 400-600 DEG C for 30-120 minutes to obtain a precipitate B; (3) adding the precipitate B into a pickling solution with the pH value of 0.5-3.0, and stirring to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid or hydrochloric acid; and (4) drying the precipitate at the temperature of 120 to 500 DEG C, so as to obtain vanadium pentoxide. According to the method, the high-purity vanadium pentoxide product can be prepared from the high-phosphorus manganese-containing acidic vanadium liquid, and phosphorus in the product can be reduced to 0.012% or below.

Description

Technical Field

[0001] The invention relates to the technical field of vanadium hydrometallurgy, in particular to a method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid. Background Art

[0002] As an important micro-alloying element, vanadium is widely used in metallurgy, chemical industry, aerospace and other fields. It can significantly improve the strength, toughness and ductility of steel, providing important support for ensuring the quality of key national projects.

[0003] In the process of extracting vanadium from vanadium-containing materials, a vanadium-extracting raw material containing high calcium, high phosphorus and manganese is involved. During the roasting-leaching process, vanadium, phosphorus and manganese will be leached into the solution at the same time to form a high-phosphorus and high-manganese acidic vanadium-containing solution. Among them, P is an important harmful element that affects the purity and vanadium precipitation rate of the product. It is difficult to remove phosphorus using ordinary chemical impurity removal methods. Even if phosphorus can be removed, vanadium will enter the precipitate, resulting in a large loss of vanadium. In addition, the manganese-containing acid leaching vanadium solution also has the problem of high manganese content in the product during the vanadium precipitation process.

[0004] At present, the vanadium precipitation process in the industrial vanadium extraction process is mainly chemical precipitation, including hydrolysis precipitation, ammonium salt precipitation, iron salt precipitation, etc. Hydrolysis precipitation is to add acid to the vanadium-containing solution to make the vanadate ions aggregate to form decavanadate ions, which are finally hydrolyzed to form H 6 V 10 O 28 Precipitation, i.e. hydration of vanadium pentoxide, is simple to operate, has low production costs, and allows vanadium concentration to fluctuate in a wide range. The disadvantage is that the product purity is low, and it has now been basically replaced by ammonium salt precipitation. Most ammonium salt precipitation is acidic ammonium salt precipitation, which is to add ammonium salt to vanadium solution. Ammonium ions can combine with vanadium oxide ions to form ammonium meta / polyvanadate precipitates. This method can obtain products with higher purity and high vanadium precipitation rate, but it is not effective in removing impurities P in the solution, and ammonium-containing vanadium precipitation wastewater needs to be treated later. The iron salt precipitation process is to mix vanadium solution with iron salt solution, heat and stir to precipitate vanadium to obtain a green solid product. The composition of the product is complex and the purity of the vanadium product is low. Chinese patent application CN 2020105365110 discloses a method for preparing high-purity vanadium pentoxide by ammonium-free vanadium precipitation in vanadium liquid, which method comprises the following steps: step a: hydrolyzing and precipitating vanadium in vanadium liquid using an ammonium-free vanadium precipitation agent, and obtaining a hydrolyzed vanadium precipitation product after solid-liquid separation; step b: purifying the hydrolyzed vanadium precipitation product using a dilute organic acid solution, and obtaining a purified hydrolyzed vanadium precipitation product after solid-liquid separation and washing; step c: calcining the purified hydrolyzed vanadium precipitation product to obtain high-purity vanadium pentoxide. The method involved in this invention is aimed at sodium vanadium liquid or acidic vanadium liquid, and uses an ammonium-free vanadium precipitation agent such as sulfuric acid to hydrolyze and precipitate vanadium in vanadium liquid, so that ammonium ions are not introduced into the vanadium precipitation process, and the vanadium precipitation wastewater is easy to treat, but it is more difficult to precipitate vanadium and remove impurities. The method is used for high-phosphorus manganese-containing acidic vanadium liquid, and the phosphorus removal effect is not good.

[0005] Chinese patent application CN202011182648 provides a method for extracting vanadium from high-phosphoric acid vanadium liquid and recycling wastewater. The method comprises: a: adding an oxidant (at least one of ammonium persulfate, sodium persulfate, sodium chlorate, potassium chlorate and hydrogen peroxide) to the high-phosphoric acid vanadium liquid, then filtering to obtain a vanadium liquid, and then extracting to obtain a vanadium-rich organic phase and a raffinate; b: returning the raffinate to the leaching process for use; c: performing a first-stage reverse extraction on part of the vanadium-rich organic phase to obtain a stripping solution, and then adding an alkaline substance to the stripping solution, and then adding the remaining vanadium-rich organic phase to perform a second-stage reverse extraction to obtain a high-concentration vanadium liquid; d: adding a vanadium precipitation agent to the high-concentration vanadium liquid for reaction, and then filtering to obtain ammonium metavanadate and a vanadium precipitation residual solution, calcining the ammonium metavanadate to obtain vanadium oxide; e: treating the vanadium precipitation residual solution with a vanadium precipitate; Pre-treatment is performed, and then the mixture is returned to step c for use; Chinese patent application CN202011182666 discloses a method for extracting vanadium from an acidic high-phosphorus vanadium liquid. The method comprises: (1) adding an oxidant (at least one of ammonium persulfate, sodium persulfate, sodium chlorate, potassium chlorate and hydrogen peroxide) to the acidic high-phosphorus vanadium liquid, reacting, and then filtering to obtain a filtered vanadium liquid; (2) adjusting the pH value of the filtered vanadium liquid obtained in step (1), heating, and then adding a vanadium precipitant (melamine, cyanuric acid and biuret), reacting, and then filtering to obtain a vanadium-rich precipitate; (3) calcining the vanadium-rich precipitate obtained in step (2) to obtain vanadium pentoxide. Both of the above patent applications use an ammonium-containing oxidant for vanadium precipitation, which not only introduces ammonium ions that are difficult to remove, but also has a poor dephosphorization effect.

[0006] Therefore, researchers have developed a method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid, aiming to solve the problems of difficult vanadium precipitation and low product purity in high-phosphorus manganese-containing vanadium liquid, which has very important economic value. Summary of the invention

[0007] The object of the present invention is to provide a method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid. The method comprises the following steps: firstly, a low-pH vanadium precipitation step is adopted to separate vanadium and phosphorus to obtain a vanadium-containing precipitate; then, the vanadium-containing precipitate is subjected to high-temperature conversion-acid washing to convert the vanadium into an oxide form; finally, impurities such as manganese and magnesium are removed by acid washing to improve the purity of the vanadium pentoxide product. The process is simple and easy to operate.

[0008] In order to achieve the above object, the present invention provides a method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid, comprising the following steps: Step (1): adding hydrochloric acid or sulfuric acid solution to the high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 0.8-1.4, stirring and reacting at 60-90° C. for 30-180 min, and performing solid-liquid separation to obtain a precipitate A and a vanadium precipitation upper layer liquid; Step (2): subjecting the precipitate A to oxidation reaction at 400-600° C. for 30-120 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 0.5-3.0 and stirring to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid or hydrochloric acid; Step (4): drying the precipitate C at 120-500° C. to obtain vanadium pentoxide.

[0009] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in step (1), the content of vanadium in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 8 g / L.

[0010] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.05 g / L.

[0011] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.5 g / L.

[0012] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in the step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 1 g / L.

[0013] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in the step (1), the manganese content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 3 g / L.

[0014] According to the method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in step (1), the pH is preferably 1.0-1.2; and in step (3), the pickling time is 10-60 min.

[0015] According to the method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in the step (3), the liquid-to-solid ratio of the pickling liquid to the precipitate B is 5-30:1 mL / g.

[0016] According to the method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in the step (3), the liquid-to-solid ratio of the pickling liquid to the precipitate B is 10-30:1 mL / g.

[0017] According to the method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention, preferably, in the step (1), the upper layer of the vanadium precipitation liquid is used as the vanadium-containing clinker leaching mother liquor.

[0018] The beneficial effects of the present invention are: The invention provides a method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid, which is mainly applicable to a vanadium recovery process for a high-phosphorus vanadium liquid. A low-pH vanadium precipitation step is firstly adopted to separate vanadium and phosphorus to obtain a vanadium-containing precipitate, and then the vanadium-containing precipitate is subjected to high-temperature conversion-acid washing to convert the vanadium into an oxide form. Finally, impurities such as manganese and magnesium are removed by acid washing to obtain a vanadium pentoxide product with a purity increased to more than 99% and a phosphorus content reduced to less than 0.012%. The process is simple and easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0020] Figure 1 The present invention is a process flow diagram of a method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid. DETAILED DESCRIPTION

[0021] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the embodiments of the present invention are further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.

[0022] When the acidic vanadium liquid that the resource utilization method of the present invention is suitable for treating uses a high-calcium, high-phosphorus, manganese-containing raw material to extract vanadium, a high-phosphorus, high-manganese acidic vanadium-containing solution, i.e., a high-phosphorus, manganese-containing acidic vanadium liquid, is formed. The vanadium liquid contains high phosphorus and manganese contents. P is an important harmful element that affects the purity of the product. Phosphorus is difficult to remove using ordinary chemical impurity removal methods. Even if phosphorus can be removed, vanadium will enter precipitation, resulting in a large loss of vanadium and reducing the vanadium precipitation rate.

[0023] The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention mainly comprises: a vanadium precipitation step, an oxidation step, a pickling step and a drying step.

[0024] The vanadium precipitation step of the present invention is: adding hydrochloric acid or sulfuric acid solution to the high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 0.8-1.4 for vanadium precipitation.

[0025] In the vanadium precipitation step of the present invention, after adjusting the pH to 0.8-1.4, stirring the reaction at 60-90° C. for 30-120 minutes to precipitate vanadium, and then performing solid-liquid separation to obtain precipitate A and vanadium precipitation upper layer liquid.

[0026] As a specific embodiment of the present invention, in the vanadium precipitation step, the vanadium content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 8 g / L. The vanadium precipitation step of the present invention can increase the vanadium precipitation rate of the low-content vanadium liquid to more than 95%.

[0027] As another specific embodiment of the present invention, in the vanadium precipitation step, the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.05 g / L; preferably, the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.5 g / L; more preferably, the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 1 g / L. The vanadium precipitation step of the present invention can effectively separate the phosphorus impurities that are most difficult to remove from the high-phosphorus manganese-containing acidic vanadium liquid, and reduce the phosphorus content in the obtained vanadium pentoxide product to less than 0.012%, thereby ensuring the product quality of vanadium pentoxide.

[0028] As another specific embodiment of the present invention, in the vanadium precipitation step, the manganese content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 3g / L. Preferably, in the vanadium precipitation step, the manganese content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 5g / L; more preferably, in the vanadium precipitation step, the manganese content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 3g / L. The method for recovering vanadium of the present invention can effectively separate manganese from the high-phosphorus manganese-containing acidic vanadium liquid, and the manganese content in the obtained vanadium pentoxide product is reduced to about 0.1%.

[0029] In the present invention, the upper layer liquid of vanadium precipitation is used as the mother liquid for leaching vanadium-containing clinker.

[0030] The oxidation step of the present invention is: oxidizing the precipitate A at 400-600° C. for 30-120 minutes to obtain the precipitate B.

[0031] The pickling step of the present invention is: adding precipitate B to a pickling solution with a pH of 0.5-3.0 and stirring to obtain precipitate C. Preferably, in the pickling step, the pickling time is 10-60 minutes; more preferably, in the pickling step, the liquid-to-solid ratio of the pickling solution to the precipitate B is 5-30:1 mL / g.

[0032] As a specific embodiment of the present invention, the liquid-to-solid ratio of the pickling solution to the precipitate B is 10-30:1 mL / g.

[0033] The drying step of the present invention is: drying the precipitate C at 120-500° C. to obtain vanadium pentoxide.

[0034] The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid of the present invention can treat the high-phosphorus manganese-containing acidic vanadium liquid produced after vanadium is extracted from high-calcium and high-phosphorus manganese-containing raw materials, effectively remove the high phosphorus content and manganese content contained in the high-phosphorus manganese-containing acidic vanadium liquid, and improve the vanadium precipitation rate to obtain high-quality vanadium pentoxide products. Among them, P is an important harmful element that affects the purity of the product. Phosphorus is difficult to remove by ordinary chemical impurity removal methods. Even if phosphorus can be removed, vanadium will enter the precipitation, resulting in a large loss of vanadium and reducing the vanadium precipitation rate of the vanadium liquid.

[0035] Example 1 A method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid in this embodiment comprises the following steps: Step (1): adding sulfuric acid solution to 200 ml of high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 1.2, stirring the reaction at 80° C. for 180 minutes, and then performing solid-liquid separation to obtain precipitate A and vanadium precipitation upper layer liquid, with a vanadium precipitation rate of 97.8%; wherein the vanadium content in the high-phosphorus manganese-containing acidic vanadium liquid is 19.81 g / L, the phosphorus content is 0.31 g / L, and the manganese content is 11.2 g / L; Step (2): subjecting the precipitate A to oxidation reaction at 500° C. for 60 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 3.0 and stirring for 40 minutes to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid, and the liquid-to-solid ratio of the pickling solution to the precipitate B is 10:1 mL / g; Step (4): drying the precipitate C at 150° C. to obtain vanadium pentoxide.

[0036] The composition of the vanadium pentoxide product obtained in Example 1 is shown in Table 1.

[0037] Example 2 A method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid in this embodiment comprises the following steps: Step (1): adding hydrochloric acid solution to 200 ml of high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 1.0, stirring the reaction at 60° C. for 90 minutes, and then performing solid-liquid separation to obtain a precipitate A and a vanadium precipitation upper layer liquid, with a vanadium precipitation rate of 96.1%; wherein the vanadium content in the high-phosphorus manganese-containing acidic vanadium liquid is 17.01 g / L, the phosphorus content is 0.78 g / L, and the manganese content is 6.05 g / L; Step (2): subjecting the precipitate A to oxidation reaction at 400° C. for 120 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 2.0 and stirring for 40 minutes to obtain a precipitate C; wherein the pickling solution is an acidic solution containing hydrochloric acid, and the liquid-to-solid ratio of the pickling solution to the precipitate B is 30:1 mL / g; Step (4): drying the precipitate C at 300° C. to obtain vanadium pentoxide.

[0038] The composition of the vanadium pentoxide product obtained in Example 2 is shown in Table 1.

[0039] Example 3 A method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid in this embodiment comprises the following steps: Step (1): adding sulfuric acid solution to 200 ml of high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 1.1, stirring the reaction at 90° C. for 60 minutes, and then performing solid-liquid separation to obtain a precipitate A and a vanadium precipitation upper layer liquid, with a vanadium precipitation rate of 95.9%; wherein the vanadium content in the high-phosphorus manganese-containing acidic vanadium liquid is 11.92 g / L, the phosphorus content is 1.52 g / L, and the manganese content is 3.27 g / L; Step (2): oxidizing the precipitate A at 600° C. for 30 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 0.5 and stirring for 10 minutes to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid, and the liquid-to-solid ratio of the pickling solution to the precipitate B is 20:1 mL / g; Step (4): drying the precipitate C at 500° C. to obtain vanadium pentoxide.

[0040] The composition of the vanadium pentoxide product obtained in Example 3 is shown in Table 1.

[0041] Comparative Example 1 The components and contents of the high-phosphorus manganese-containing acidic vanadium liquid treated in this comparative example are the same as those in Example 1, and the specific steps are as follows: Step (1): adding sulfuric acid solution to 200 ml of high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 1.8, stirring and reacting at 95° C. for 60 minutes, and then performing solid-liquid separation to obtain precipitate A and vanadium precipitation upper layer liquid, with a vanadium precipitation rate of 76.9%; Step (2): subjecting the precipitate A to oxidation reaction at 500° C. for 60 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 3.0 and stirring for 40 minutes to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid, and the liquid-to-solid ratio of the pickling solution to the precipitate B is 10:1 mL / g; Step (4): drying the precipitate C at 150° C. to obtain vanadium pentoxide.

[0042] The composition of the vanadium pentoxide product obtained in Comparative Example 1 is shown in Table 1.

[0043] Table 1 Vanadium pentoxide product composition / %

[0044] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the embodiments of the present invention as described above, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.

Claims

1. A method for recovering vanadium from a high-phosphorus manganese-containing acidic vanadium liquid, characterized in that: The steps include: Step (1): adding hydrochloric acid or sulfuric acid solution to the high-phosphorus manganese-containing acidic vanadium liquid to adjust the pH to 0.8-1.4, stirring and reacting at 60-90° C. for 30-180 min, and performing solid-liquid separation to obtain a precipitate A and a vanadium precipitation upper layer liquid; Step (2): subjecting the precipitate A to oxidation reaction at 400-600° C. for 30-120 min to obtain a precipitate B; Step (3): adding the precipitate B to a pickling solution with a pH of 0.5-3.0 and stirring to obtain a precipitate C; wherein the pickling solution is an acidic solution containing sulfuric acid or hydrochloric acid; Step (4): drying the precipitate C at 120-500° C. to obtain vanadium pentoxide.

2. A method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the vanadium content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 8 g / L.

3. A method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.05 g / L.

4. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 0.5 g / L.

5. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the phosphorus content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 1 g / L.

6. A method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 2, characterized in that: In the step (1), the manganese content in the high-phosphorus manganese-containing acidic vanadium liquid is not less than 3 g / L.

7. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the pH is preferably 1.0-1.2; in the step (3), the pickling time is 10-60 min.

8. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 3, characterized in that: In the step (3), the liquid-to-solid ratio of the pickling solution to the precipitate B is 5-30:1 mL / g.

9. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (3), the liquid-to-solid ratio of the pickling solution to the precipitate B is 10-30:1 mL / g.

10. The method for recovering vanadium from high-phosphorus manganese-containing acidic vanadium liquid according to claim 1, characterized in that: In the step (1), the upper layer of the vanadium precipitation liquid is used as the mother liquid for leaching vanadium-containing clinker.

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