CN113957262B - Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium - Google Patents
Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium Download PDFInfo
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Abstract
The invention relates to a method for precipitating vanadium from a vanadium-chromium leaching solution without ammonium, which is a method for precipitating vanadium from a vanadium-chromium leaching solution without ammonium based on the steps of vanadium precipitation by manganese, acid leaching and vanadium precipitation by hydrolysis, and the method comprises the steps of putting manganese salt into the vanadium-chromium leaching solution to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater; performing acid leaching on the manganese vanadate precipitate to obtain vanadium-containing manganic acid leaching solution; adjusting the pH value and the precipitation temperature of the pickle liquor to obtain a red cake and manganese-containing hydrolysis vanadium precipitation wastewater; dehydrating and drying the red cake to obtain vanadium pentoxide; adding a reducing agent into the chromium-manganese-containing vanadium precipitation wastewater, adjusting the pH value to precipitate chromium, filtering to obtain chromium hydroxide precipitate, and roasting to obtain chromium sesquioxide; and (3) evaporating and crystallizing the manganese-containing hydrolysis vanadium precipitation wastewater to obtain manganese salt, and returning the manganese salt to the precipitation process to be used as a subsequent vanadium precipitation additive. The method realizes the high-efficiency separation of the vanadium and the chromium without ammonium precipitation in the vanadium slag leaching solution, the prepared vanadium pentoxide has high purity, and the additive manganese salt can be recycled, thereby effectively saving the production cost.
Description
Technical Field
The invention relates to a method for precipitating vanadium from a vanadium-chromium leaching solution without ammonium, belonging to the technical field of vanadium chemical engineering and resource recycling.
Background
Vanadium is an important strategic metal in China, and vanadium and compounds thereof are widely applied to the fields of metallurgy, chemical engineering, aerospace and the like. Vanadium titano-magnetite is the most important vanadium extraction in the world at presentThe raw materials, 88% of the annual vanadium yield, are all from vanadium titano-magnetite. After the ore is ironed by a blast furnace and oxygen is blown by a converter, most of vanadium is enriched in vanadium slag, and the grade of the vanadium (as V) in the vanadium slag 2 O 5 Calculated) can reach 10-14 percent. In addition, because the properties of chromium in the schreyerite are similar to those of vanadium, the chromium also enters vanadium slag after the flow of a blast furnace-converter. Chromium grade (in terms of Cr) especially for high chromium vanadium titano-magnetite 2 O 3 Calculated) can reach 9% -13%.
At present, the most main process for extracting vanadium from vanadium slag is a sodium roasting-water leaching process. The sodium salt is used for converting stable spinel phase sodium oxide in the vanadium slag into water-soluble sodium vanadate, so that vanadium is transferred into a liquid phase after water leaching, and meanwhile, chromium also enters a leaching solution in the form of sodium chromate. In addition, the leachate also contains a large amount of sodium ions and a small amount of iron and silicon ions. For vanadium-chromium leaching solution, the vanadium precipitation technology which is industrialized at present is ammonium salt vanadium precipitation, the vanadium precipitation efficiency of the technology is high, and the process is short. But the technology will generate a lot of ammonia nitrogen waste water and pollute the environment. Therefore, a new ammonium-free vanadium precipitation process is urgently needed.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a method for precipitating vanadium in a vanadium-chromium leaching solution without ammonium, which is based on the method for precipitating vanadium in a vanadium-chromium leaching solution without ammonium and precipitating vanadium in the steps of manganization vanadium precipitation, acid leaching and hydrolysis vanadium precipitation, and realizes high-efficiency precipitation of vanadium in the vanadium-chromium leaching solution, high-efficiency separation of vanadium and chromium and no ammonification of wastewater, and simultaneously realizes cyclic utilization of a vanadium precipitation additive and vanadium precipitation wastewater, thereby reducing the production cost and solving the problem of water body pollution.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a method for precipitating vanadium from a vanadium-chromium leaching solution without ammonium comprises the following steps:
s1, adding manganese salt into the vanadium-chromium leaching solution to precipitate vanadium, and then filtering to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater;
s2, performing acid leaching on the manganese vanadate precipitate obtained in the step S1 to obtain vanadium-manganese-containing leachate;
s3, adjusting the pH value of the vanadium-manganese containing leachate obtained in the step S2, hydrolyzing to precipitate vanadium, and filtering to obtain red cakes and manganese-containing hydrolysis vanadium precipitation wastewater;
s4, drying and dehydrating the red cake obtained in the step S3 to obtain a vanadium pentoxide product;
s5, adding a reducing agent into the chromium-containing vanadium precipitation wastewater obtained in the step S1 for reduction, adjusting the pH value to precipitate chromium, and filtering and separating solid and liquid to obtain chromium hydroxide precipitate and chromium extraction waste liquid;
s6, roasting the chromium hydroxide precipitate obtained in the step S5 to obtain chromium sesquioxide;
s7, evaporating and crystallizing the manganese-containing hydrolysis vanadium precipitation wastewater obtained in the step S3, extracting manganese element in a manganese salt form, and obtaining manganese-extracted wastewater.
In the method, preferably, in step S1, the vanadium-chromium leaching solution is obtained by leaching vanadium slag or vanadium-chromium slag after sodium roasting; the leaching solution contains vanadium ions, chromium ions, sodium ions and silicon ions.
The pH value of the vanadium-chromium leaching solution is 8-11; the manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate, preferably manganese sulfate; the molar ratio of the manganese element in the manganese salt calculated by MnO to the vanadium element in the vanadium-chromium leaching solution calculated by V is 0.25-3, wherein the most preferable molar ratio is 0.5-1.5.
Through a large amount of use researches, the molar ratio of manganese in manganese salt calculated by MnO to vanadium in the vanadium-chromium leaching solution calculated by V is too small, so that the manganese salt is insufficient in addition, and further, all vanadium in the leaching solution cannot be ensured to be precipitated; the molar ratio is preferably 0.25 to 3, and most preferably 0.5 to 1.5, because too large a molar ratio may result in excessive manganese salt in the leachate, which may cause cost consumption, and may result in a large amount of manganese ions remaining in the vanadium precipitation wastewater. In the method, preferably, in step S1, the temperature for precipitating vanadium is between room temperature and 100 ℃, and the precipitation time is between 5 and 120 min.
The method as described above, preferably, in step S2, the pickling process is performed in a water bath or a heating jacket; the deionized water and the manganese vanadate are in a liquid-solid ratio of (mL/g) 2-20: 1, leaching, and controlling the pH value of a leaching system to be 2-3 by adding an acid solution in the leaching process; the acid is at least one of sulfuric acid, hydrochloric acid or nitric acid; the temperature of acid leaching is 20-100 ℃; the time of acid leaching is 30 min-180 min.
According to the method, preferably, in step S3, the hydrolysis vanadium precipitation process is free of any vanadium precipitation additive, and the precipitation of vanadium is achieved only by adjusting the pH and precipitation temperature of the vanadium-chromium leachate, and the pH of the system is maintained to be 1.5-2.5 by adding acid in the hydrolysis vanadium precipitation process; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid; the temperature of the hydrolysis vanadium precipitation is 80-100 ℃, and the time of the vanadium precipitation is 30-180 min; after the solid-liquid separation of the precipitate is completed, the red cake is repeatedly washed by water.
In the method as described above, preferably, in step S4, the red cake is dried at 80-120 ℃ in advance; the drying time is 5-24 h; further drying and dehydrating at the temperature of 200-600 ℃; the dehydration time is 30 min-300 min.
In the method as described above, preferably, in step S5, the reducing agent is at least one of sodium sulfite, sodium sulfide, sodium metabisulfite, and sodium thiosulfate; the mass ratio of the reducing agent to chromium in the chromium-containing vanadium precipitation wastewater is 3-6: 1; the reduction temperature is between room temperature and 100 ℃; the reduction time is 20-120 min; after the reduction is finished, adjusting the pH value to be within the range of 7-10 by using a sodium hydroxide solution, and precipitating chromium in a chromium hydroxide form; the precipitation temperature is 20-100 ℃; the precipitation time is 30-300 min; after precipitation, solid-liquid separation is carried out to obtain chromium hydroxide precipitation and chromium extraction waste liquid. The waste liquid from chromium extraction contains a large amount of sodium ions, and sodium can be recovered in the form of sodium salt through evaporation and crystallization.
As described above, preferably, in step S6, the process of roasting the chromium hydroxide precipitate is performed in a muffle furnace; the roasting temperature is 900-1200 ℃; the roasting time is 30-300 min; and grinding the roasted clinker to be less than 300 meshes to obtain a chromium sesquioxide product.
In the method, preferably, in step S7, the manganese salt in the manganese-containing hydrolysis vanadium precipitation wastewater is recovered by evaporative crystallization.
In the method, preferably, the manganese salt obtained in the step S7 can be used as an additive for precipitating vanadium from the manganese salt in the next reaction step S1, so that the manganese salt additive can be recycled, and the manganese extraction wastewater can be used as an acid leaching medium in the next reaction step S2, so that the resource recycling is realized, and the production cost is greatly saved.
(III) advantageous effects
The invention has the beneficial effects that:
according to the method for precipitating vanadium from the vanadium-chromium leaching solution without ammonium, provided by the invention, the vanadium-chromium leaching solution is used as a raw material, the ammonium-free precipitation of vanadium is used as a starting point, the vanadium is efficiently extracted from the leaching solution and the vanadium and the chromium are efficiently separated by precipitating the vanadium from the manganese salt, and finally the obtained product can be recycled, so that the resources are saved, and the production cost is greatly reduced.
The method of the invention has the following advantages:
(1) the manganese salt has high selectivity on vanadium, and can realize high-efficiency separation and extraction of vanadium in the vanadium-chromium leaching solution;
(2) no impurity ions are introduced in the vanadium precipitation process, manganese can be further recovered after the vanadium precipitation by hydrolysis, and can be recycled as an additive in the vanadium precipitation process of the manganese salt;
(3) the tailings produced in the precipitation and acid leaching process of the manganese vanadate have extremely low yield and are easy to process subsequently.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The method fully utilizes the strong selectivity of manganese salt to vanadium to extract vanadium from the vanadium-chromium leaching solution, and further transfers the vanadium into acid leaching solution in an acid leaching mode. The separation of vanadium from impurity elements such as sodium, silicon, iron and the like in the vanadium-chromium leaching solution is realized through the modes of manganese precipitation and acid leaching. Finally, the precipitation of vanadium is realized by a method of hydrolyzing and precipitating vanadium, and the use of ammonium salt is effectively avoided. Specifically, manganese salt is added into the vanadium-chromium leaching solution to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater; performing acid leaching on the manganese vanadate precipitate to obtain vanadium-containing manganic acid leaching solution; adjusting the pH value and the precipitation temperature of the pickle liquor to obtain a red cake and manganese-containing hydrolysis vanadium precipitation wastewater; dehydrating and drying the red cake to obtain a vanadium pentoxide product; adding a reducing agent into the chromium-manganese-containing vanadium precipitation wastewater, adjusting the pH value to precipitate chromium, filtering to obtain chromium hydroxide precipitate, and roasting to obtain a chromium sesquioxide product; and hydrolyzing the vanadium precipitation wastewater containing manganese, evaporating and crystallizing to obtain manganese salt, and returning the manganese salt to the precipitation process to be used as a subsequent vanadium precipitation additive.
For a better understanding of the present invention, reference will now be made in detail to the present embodiments of the invention, which are illustrated in the accompanying drawings.
Example 1
A method for precipitating vanadium and no ammonium by using manganese salt in vanadium-chromium leaching solution is shown in a process flow as shown in figure 1 and comprises the following steps:
(1) vanadium precipitation by manganese salt: the pH value of the vanadium-chromium leaching solution is 9.26, wherein the concentrations of vanadium, chromium, sodium, silicon and iron ions are respectively 13.2g/L, 0.32g/L, 8.25g/L, 0.50g/L and 0.29 mg/L. Adding manganese sulfate into the vanadium-chromium leaching solution to precipitate vanadium, wherein the molar ratio of manganese sulfate calculated by MnO to vanadium calculated by V in the vanadium-chromium leaching solution is 1, the vanadium precipitation temperature is room temperature, and the vanadium precipitation time is 30 min. And filtering after the vanadium precipitation of the manganese salt is finished to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater. The vanadium precipitation rate of the manganese salt is 97.35 percent and the chromium with the concentration of 99.32 percent is remained in the chromium-containing wastewater through analyzing the content of residual vanadium and the concentration of chromium ions in the chromium-containing vanadium precipitation wastewater.
(2) Acid leaching: the manganese vanadate leaching process is carried out in a water bath kettle, deionized water is added into a leaching container at first by taking the ratio of deionized water to manganese vanadate precipitate as 5 in mL/g according to the liquid-solid ratio, manganese vanadate is added when the temperature reaches 60 ℃, and the pH value of a leaching system is controlled to be about 2.5 by adding sulfuric acid with the volume fraction of 10%; the leaching temperature is 60 ℃; the leaching process time is 30 min; after leaching, solid-liquid separation is carried out to obtain leaching solution containing vanadium and manganese with little tailings.
(3) And (3) hydrolyzing to precipitate vanadium: and (3) carrying out a vanadium precipitation process on the vanadium-manganese-containing leaching solution in a water bath, wherein in the hydrolysis process, the pH value of a vanadium precipitation system is controlled to be about 1.8 by adding a sulfuric acid solution with the volume fraction of 10%, the vanadium precipitation temperature is 100 ℃, and the vanadium precipitation time is 60 min. And filtering after hydrolyzing to precipitate vanadium to obtain red cakes and manganese-containing hydrolysis vanadium precipitation wastewater, and determining the content of vanadium in the manganese-containing hydrolysis vanadium precipitation wastewater to obtain the hydrolysis vanadium precipitation rate of 95.52%.
(4) Preparing a vanadium product: and drying the red cake at 100 ℃ for 24 hours in advance, and then roasting at 300 ℃ for 60 minutes to obtain the vanadium pentoxide with the purity of 98.20% after washing.
(5) Reduction and precipitation of chromium: adding a reducing agent into the chromium-containing vanadium precipitation wastewater obtained in the step (1) for reduction, wherein the reducing agent is selected from sodium metabisulfite; the mass ratio of the sodium pyrosulfite to the chromium in the chromium-containing vanadium precipitation wastewater is 2.5; the reduction temperature is 70 ℃; the reduction time is 60 min; after reduction, adjusting the pH value to be 7-9 by adding sodium hydroxide, and precipitating chromium in the form of chromium hydroxide; the precipitation temperature is 80 ℃; precipitating for 60 min; after precipitation, solid-liquid separation is carried out to obtain chromium hydroxide precipitation and chromium extraction waste liquid, and the reduction rate of chromium is calculated to be 98.85%.
(6) Preparing a chromium product: roasting the chromium hydroxide precipitate obtained in the step (5) at 900 ℃ for 60 min; grinding to below 300 meshes to obtain the chromium sesquioxide with the purity of 89.90 percent.
(7) And (3) evaporating and crystallizing manganese: and (4) carrying out evaporative crystallization on the manganese-containing hydrolysis vanadium precipitation wastewater obtained in the step (3), and crystallizing for 120min to obtain manganese sulfate crystals and manganese extraction wastewater.
(8) Waste liquid circulation: the chromium precipitation wastewater in the step (5) contains a large amount of sodium ions, and sodium can be recovered in a sodium salt form through evaporative crystallization; the manganese extraction wastewater obtained in the step (7) can be recycled to be used as an acid leaching medium of manganese vanadate in the next reaction step (2); the obtained manganese sulfate crystal is used as an additive for precipitating vanadium from manganese salt in the step (1) of the next reaction, thereby realizing the recycling of the manganese salt additive.
Example 2
A method for precipitating vanadium and no ammonium by using manganese salt in vanadium-chromium leaching solution is shown in a process flow as shown in figure 1 and comprises the following steps:
(1) vanadium precipitation by manganese salt: the pH value of the vanadium-chromium leaching solution is 9.26, wherein the concentrations of vanadium, chromium, sodium, silicon and iron ions are respectively 13.2g/L, 0.32g/L, 8.25g/L, 0.50g/L and 0.29 mg/L. Adding manganese sulfate into the vanadium-chromium leaching solution to precipitate vanadium, wherein the molar ratio of manganese to vanadium in the vanadium-chromium leaching solution is 1.5 in terms of MnO, the vanadium precipitation temperature is 60 ℃, and the vanadium precipitation time is 60 min. And filtering after the vanadium precipitation of the manganese salt is finished to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater. The vanadium precipitation rate of the manganese salt is 98.37 percent and 98.25 percent of chromium is left in the chromium-containing wastewater by analyzing the content of residual vanadium and the concentration of chromium ions in the chromium-containing vanadium precipitation wastewater.
(2) Acid leaching: the leaching process of manganese vanadate is carried out in a water bath kettle, deionized water and manganese vanadate are added into a leaching container according to the liquid-solid ratio of 10 in mL/g, manganese vanadate is added at 50 ℃, and the pH value of a leaching system is controlled to be about 2.8 by adding sulfuric acid with the volume fraction of 20%; the leaching temperature is 50 ℃; the leaching process time is 60 min; after leaching, solid-liquid separation is carried out to obtain leaching solution containing vanadium and manganese with little tailings.
(3) And (3) hydrolyzing to precipitate vanadium: the vanadium precipitation process is carried out in a water bath, the hydrolysis process is carried out by adding sulfuric acid solution with volume fraction of 20% to control the pH value of a vanadium precipitation system of the vanadium-manganese containing leaching solution to be about 2.0, the vanadium precipitation temperature is 90 ℃, and the vanadium precipitation time is 40 min. And filtering after hydrolysis vanadium precipitation to obtain red cakes and manganese-containing hydrolysis vanadium precipitation wastewater, and measuring the content of vanadium in the manganese-containing hydrolysis vanadium precipitation wastewater to obtain the hydrolysis vanadium precipitation rate of 94.88%.
(4) Preparing a vanadium product: and drying the red cake at 100 ℃ for 24 hours in advance, and then roasting at 300 ℃ for 60 minutes to obtain the vanadium pentoxide with the purity of 97.30% after washing.
(5) Reducing and precipitating chromium: adding a reducing agent into the chromium-containing vanadium precipitation wastewater obtained in the step (1) for reduction, wherein the reducing agent is selected from sodium sulfite; the mass ratio of the sodium sulfite to the chromium in the chromium-containing vanadium precipitation wastewater is 4; the reduction temperature is 80 ℃; the reduction time is 60 min; after the reduction is finished, the pH value is adjusted to be within the range of 8-9 by adding sodium hydroxide to precipitate chromium in the form of chromium hydroxide; the precipitation temperature is 90 ℃; settling time is 120 min; after precipitation, solid-liquid separation is carried out to obtain chromium hydroxide precipitation and chromium extraction waste liquid, wherein the reduction rate of chromium is 97.44%.
(6) Preparing a chromium product: roasting the chromium hydroxide precipitate obtained in the step (5) at 1000 ℃ for 60 min; grinding to below 300 meshes to obtain the chromium sesquioxide with the purity of 92.13 percent.
(7) And (3) evaporating and crystallizing manganese: and (4) carrying out evaporative crystallization on the manganese-containing hydrolysis vanadium precipitation wastewater obtained in the step (3), and crystallizing for 120min to obtain manganese sulfate crystals and manganese extraction wastewater.
(8) In the step (5), the chromium precipitation wastewater contains a large amount of sodium ions, and sodium can be recovered in a sodium salt form through evaporative crystallization; the manganese extraction wastewater obtained in the step (7) can be recycled to be used as a manganese vanadate acid leaching medium in the step (2) of the next reaction, and manganese sulfate crystals can be recycled to be used as a manganese salt additive in the step (1) of the next reaction.
Example 3
A method for precipitating vanadium and no ammonium by using manganese salt in vanadium-chromium leaching solution is shown in a process flow as figure 1 and comprises the following steps:
(1) vanadium precipitation by manganese salt: the pH value of the vanadium-chromium leaching solution is 9.26, wherein the concentrations of vanadium, chromium, sodium, silicon and iron ions are respectively 13.2g/L, 0.32g/L, 8.25g/L, 0.50g/L and 0.29 mg/L. Adding manganese sulfate into the vanadium-chromium leaching solution to precipitate vanadium, wherein the molar ratio of manganese to vanadium in the vanadium-chromium leaching solution is 0.75 in terms of MnO, the vanadium precipitation temperature is 80 ℃, and the vanadium precipitation time is 120 min. And filtering after the vanadium precipitation of the manganese salt is finished to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater. The vanadium precipitation rate of the manganese salt can be 99.12 percent by analyzing the content of residual vanadium and the concentration of chromium ions in the chromium-containing vanadium precipitation wastewater, and 97.33 percent of chromium is remained in the chromium-containing wastewater.
(2) Acid leaching: the leaching process of manganese vanadate is carried out in a water bath kettle, deionized water and manganese vanadate are added into a leaching container according to the liquid-solid ratio of mL/g being 15, manganese vanadate is added at 70 ℃, and the pH value of a leaching system is controlled to be about 2.6 by adding sulfuric acid with the volume fraction of 20%; the leaching temperature is 70 ℃; the leaching process time is 60 min; after leaching, solid-liquid separation is carried out to obtain leaching solution containing vanadium and manganese with little tailings.
(3) And (3) hydrolyzing to precipitate vanadium: the vanadium precipitation process is carried out in a water bath, the hydrolysis process is carried out by adding sulfuric acid solution with volume fraction of 20% to control the pH value of a vanadium precipitation system of the vanadium-manganese containing leaching solution to be about 1.5, the vanadium precipitation temperature is 90 ℃, and the vanadium precipitation time is 90 min. And filtering after hydrolysis vanadium precipitation to obtain a red cake and manganese-containing hydrolysis vanadium precipitation wastewater, and determining the content of vanadium in the manganese-containing hydrolysis vanadium precipitation wastewater to obtain the hydrolysis vanadium precipitation rate of 96.23%.
(4) Preparing a vanadium product: the red cake is dried at 120 ℃ for 20 hours in advance, and then is roasted at 280 ℃ for 120 minutes to obtain vanadium pentoxide with the purity of 98.32 percent after washing.
(5) Reducing and precipitating chromium: adding a reducing agent into the chromium-containing vanadium precipitation wastewater obtained in the step (1) for reduction, wherein the reducing agent is selected from sodium thiosulfate; the mass ratio of the sodium thiosulfate to the chromium in the chromium-containing vanadium precipitation wastewater is 5; the reduction temperature is 50 ℃; the reduction time is 60 min; after the reduction is finished, the pH value is adjusted to be within the range of 8-9 by adding sodium hydroxide to precipitate chromium in the form of chromium hydroxide; the precipitation temperature is 50 ℃; the precipitation time is 30 min; after precipitation, solid-liquid separation is carried out to obtain chromium hydroxide precipitate and chromium extraction waste liquid, wherein the reduction rate of chromium is 94.28%.
(6) Preparing a chromium product: roasting the chromium hydroxide precipitate obtained in the step (5) at 1000 ℃ for 60 min; grinding to below 300 meshes to obtain the chromium sesquioxide with the purity of 94.10 percent.
(7) And (3) evaporating and crystallizing manganese: and (4) evaporating and crystallizing the manganese-containing hydrolysis vanadium precipitation wastewater obtained in the step (3), and crystallizing for 120min to obtain manganese sulfate crystals and manganese extraction wastewater.
The manganese sulfate crystal obtained in the step can be recycled to be used in the next process of vanadium precipitation and ammonium-free of manganese salt in vanadium-chromium leaching solution.
(8) The chromium precipitation wastewater in the step (5) contains a large amount of sodium ions, and sodium can be recovered in a sodium salt form through evaporative crystallization; the manganese extraction wastewater obtained in the step (7) can be recycled to be used as a manganese vanadate acid leaching medium in the step (2) of the next reaction, and manganese sulfate crystals can be recycled to be used as a manganese salt additive in the step (1) of the next reaction.
Comparative example 1
The method comprises the steps of directly hydrolyzing vanadium precipitation in a vanadium-chromium leaching solution with the pH value of 9.26 and the concentrations of vanadium, chromium, sodium, silicon and iron ions of 13.2g/L, 0.32g/L, 8.25g/L, 0.50g/L and 0.29mg/L respectively, wherein the vanadium precipitation process is carried out in a water bath, the pH value of the vanadium precipitation is controlled to be about 1.8 by adding a sulfuric acid solution with the volume fraction of 10%, the vanadium precipitation time is 60min, the vanadium precipitation rate is only 93.10%, and a vanadium pentoxide product contains a large amount of sodium, chromium and silicon impurities.
Comparative example 2
The vanadium-chromium leachate with the pH value of 9.26 and the concentrations of vanadium, chromium, sodium, silicon and iron ions of 13.2g/L, 0.32g/L, 8.25g/L, 0.50g/L and 0.29mg/L is subjected to calcification vanadium precipitation, acid leaching vanadium precipitation and hydrolysis vanadium precipitation, a large amount of calcium sulfate is generated in the acid leaching process, the waste of a calcium salt additive is caused, and the calcium salt additive is difficult to recycle.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art can change or modify the technical content disclosed above into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for precipitating vanadium from a vanadium-chromium leaching solution without ammonium is characterized by comprising the following steps:
s1, adding manganese salt into the vanadium-chromium leaching solution to precipitate vanadium, and then filtering to obtain manganese vanadate precipitate and chromium-containing vanadium precipitation wastewater;
s2, performing acid leaching on the manganese vanadate precipitate obtained in the step S1 to obtain vanadium-manganese-containing leachate;
s3, adjusting the pH value of the vanadium-manganese containing leachate obtained in the step S2, hydrolyzing to precipitate vanadium, and filtering to obtain red cakes and manganese-containing hydrolysis vanadium precipitation wastewater;
s4, drying and dehydrating the red cake obtained in the step S3 to obtain a vanadium pentoxide product;
s5, reducing the chromium-containing vanadium precipitation wastewater obtained in the step S1 by adding a reducing agent, adjusting the pH value to precipitate chromium, and filtering and separating solid and liquid to obtain chromium hydroxide precipitate and chromium extraction waste liquid;
s6, roasting the chromium hydroxide precipitate obtained in the step S5 to obtain chromium sesquioxide;
s7, evaporating and crystallizing the manganese-containing hydrolysis vanadium precipitation wastewater obtained in the step S3 to extract manganese element in the form of manganese salt;
in step S1, the pH value of the vanadium-chromium leaching solution is 8-11; the manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate.
2. The method according to claim 1, wherein in step S1, the vanadium-chromium leaching solution is a leaching solution obtained by leaching vanadium slag or vanadium-chromium slag after sodium roasting; the leaching solution contains vanadium ions, chromium ions, sodium ions and silicon ions.
3. The method of claim 1,
the manganese salt precipitator is used in such a way that the molar ratio of manganese element in manganese salt counted by MnO to vanadium element in the vanadium-chromium leaching solution counted by V is 0.25-3.
4. The method of claim 1, wherein in step S1, the temperature for precipitating vanadium is between room temperature and 100 ℃, and the precipitation time is between 5 and 120 min.
5. The method of claim 1, wherein in step S2, the pickling process is performed in a water bath or a heating jacket; the deionized water and the manganese vanadate are in a liquid-solid ratio of (mL/g) 2-20: 1, leaching, and controlling the pH value of a leaching system to be 2-3 by adding an acid solution in the leaching process; the acid is at least one of sulfuric acid, hydrochloric acid or nitric acid; the temperature of acid leaching is 20-100 ℃; the time of acid leaching is 30 min-180 min.
6. The method of claim 1, wherein in step S3, the pH of the system is maintained at 1.5-2.5 by adding acid during the hydrolysis vanadium precipitation process; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid; the temperature of hydrolysis vanadium precipitation is 80-100 ℃, and the time of vanadium precipitation is 30-180 min.
7. The method as claimed in claim 1, wherein the red cake is previously dried at 80-120 ℃ in step S4; the drying time is 5-24 h; further drying and dehydrating at the temperature of 200-600 ℃; the dehydration time is 30 min-300 min.
8. The method of claim 1, wherein in step S5, the reducing agent is at least one of sodium sulfite, sodium sulfide, sodium metabisulfite, sodium thiosulfate; the mass ratio of the reducing agent to chromium in the chromium-containing vanadium precipitation wastewater is 3-6: 1; the reduction temperature is between room temperature and 100 ℃; the reduction time is 20-120 min; after the reduction is finished, adjusting the pH value to be within the range of 7-10 by using a sodium hydroxide solution, and precipitating chromium in a chromium hydroxide form; the precipitation temperature is 20-100 ℃; the precipitation time is 30-300 min.
9. The method of claim 1, wherein in the step S6, the roasting temperature is 900-1200 ℃; the roasting time is 30-300 min.
10. The method of claim 1, wherein the manganese salt obtained in step S7 is used as an additive for vanadium precipitation from the manganese salt in the next reaction step S1, thereby recycling the manganese salt additive, and the manganese extraction wastewater can be used as an acid leaching medium in the next reaction step S2.
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