CN109666789B - Method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate - Google Patents
Method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate Download PDFInfo
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Abstract
The invention relates to a method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate, which comprises the steps of mixing the vanadium-chromium slag and the manganese carbonate to obtain a mixed material, and roasting the mixed material at high temperature to obtain a roasted clinker; leaching in acid solution, and filtering to obtain vanadium-containing leaching solution and chromium-containing leaching slag; regulating the pH value and the precipitation temperature and time of the obtained vanadium-containing leaching solution to precipitate vanadium, and filtering to obtain ammonium polyvanadate precipitate and manganese-containing supernatant; precipitating ammonium polyvanadate obtained by roasting to obtain a vanadium pentoxide product; carbonizing the manganese-containing supernatant, and filtering to obtain manganese carbonate precipitate and vanadium precipitation waste liquid; the manganese carbonate is recycled to the roasting system to be used as a roasting additive to participate in the next roasting; and after removing impurities from the vanadium precipitation waste liquid, recycling the vanadium precipitation waste liquid back to a leaching system to be used as a leaching medium. The method realizes the high-efficiency separation of vanadium and chromium in the high-chromium vanadium slag, the prepared vanadium pentoxide has high purity, the additive manganese carbonate can be recycled, the vanadium precipitation waste liquid can be recycled, and the production cost is effectively saved.
Description
Technical Field
The invention relates to a method for preparing vanadium pentoxide from vanadium-chromium slag and manganese carbonate, belonging to the technical field of vanadium chemical engineering and resource recycling.
Background
Vanadium and chromium are important rare metals, and compounds of the vanadium and chromium are widely applied to the fields of metallurgy, chemical industry, building materials and the like. The vanadium-chromium slag is a byproduct in the smelting process of the high-chromium vanadium titano-magnetite, wherein vanadium and chromium have relatively high grade, so the vanadium-chromium slag is a potential vanadium-chromium extraction raw material. At present, the main processes for extracting vanadium from vanadium slag are a sodium roasting water leaching process and a calcification roasting acid leaching process, and the two industries are generally applicable to low-chromium vanadium slag at present. For the vanadium extraction process of vanadium-chromium slag, sodium roasting and calcification roasting face inevitable problems.
Although the sodium salt roasting water immersion process of the vanadium chromium slag has low cost and simple process, the roasting process can cause material sintering and ring formation in the furnace due to the melting of sodium salt. Meanwhile, sodium vanadate and sodium chromate which are dissolved in water are generated after the vanadium and the chromium are subjected to sodium treatment and are transferred into a liquid phase, and the vanadium and the chromium are difficult to separate due to the similar properties of the vanadium and the chromium. In addition, the vanadium extraction tailings obtained by sodium salt roasting water leaching have high alkali metal content, so that the iron element cannot be effectively utilized. The vanadium extraction tailings and the wastewater contain a large amount of high-valence hexavalent chromium, which causes great pollution to the environment.
The calcified roasting and acid leaching of the vanadium-chromium slag is a relatively clean vanadium extraction mode, but the vanadium conversion rate is lower than that of sodium roasting, and part of the reason is that calcium sulfate precipitation is formed in the leaching process to wrap a vanadium-containing phase, so that the vanadium leaching rate is slightly lower. Meanwhile, the tailings contain sulfur elements, and if the tailings are alloyed, the content of sulfur in the alloy is too high, so that the product requirement cannot be met. Therefore, a new vanadium extraction mode needs to be further found, and the defects of the sodium roasting water leaching and calcification roasting acid leaching process need to be effectively avoided.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a method for preparing vanadium pentoxide by using vanadium-chromium slag, which can realize the high-efficiency separation and extraction of vanadium and chromium in high-chromium vanadium slag, realize the cyclic utilization of roasting additives and vanadium precipitation wastewater, reduce the production cost and solve 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 preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate comprises the following steps:
s1, roasting: mixing the vanadium-chromium slag and manganese carbonate to obtain a mixed material, and roasting the mixed material at a high temperature to obtain a roasted clinker;
s2, leaching: leaching the roasted clinker obtained in the step S1, and then filtering to obtain vanadium-containing leaching liquid and chromium-containing leaching slag;
s3, precipitating vanadium: adding a vanadium precipitation additive into the vanadium-containing leaching solution obtained in the step S2, adding an acid solution to adjust the pH value to 2-3 for vanadium precipitation, precipitating vanadium, and filtering to obtain an ammonium polyvanadate precipitate and a manganese-containing supernatant;
s4, preparing a product: roasting the ammonium polyvanadate precipitate obtained in the step S3 to obtain a vanadium pentoxide product;
s5, recovering manganese: carbonizing the manganese-containing supernatant obtained in the step S3, and then filtering to obtain manganese carbonate precipitate and vanadium extraction waste liquid;
s6, manganese cycle: the manganese carbonate precipitate is recycled to the roasting system to be used as an additive to participate in the next roasting;
s7, recycling vanadium extraction waste liquid: and (4) after the vanadium extraction waste liquid obtained in the step S5 is subjected to impurity removal, recycling the vanadium extraction waste liquid as a leaching medium in the step S2 to a leaching system.
The method as described above, preferably, in step S1, the vanadium content in the vanadium chromium slag is V2O55-20% of chromium, and the chromium content is Cr2O3The content of the vanadium chromium slag is 5-15%, the particle size of the vanadium chromium slag is 200-300 meshes, and the manganese carbonate is at least one of a manganese carbonate reagent or rhodochrosite; the dosage ratio of the vanadium chromium slag to the manganese carbonate is V in terms of vanadium in the vanadium chromium slag2O3The molar ratio of manganese to manganese in manganese carbonate is 1: 0.5 to 3.
In the method, in step S1, the high-temperature baking temperature is preferably 800 to 950 ℃ and the time is preferably 60 to 300 min.
The manganese roasting temperature is preferably 800-950 ℃, when the roasting temperature is lower than 800 ℃, only a small amount of vanadium in the vanadium slag can be converted into soluble manganese vanadate by manganese oxide, and the leaching rate is low; when the roasting temperature is higher than 950 ℃, a low-melting-point substance phase in the material is locally melted, and vanadium is wrapped to be not beneficial to leaching. Heating the material to a specified temperature along with the furnace in the roasting process, or putting the material into the furnace after the furnace temperature reaches the specified temperature; the roasting constant temperature time is 60-300 min, and when the roasting time is less than 60min, the manganese oxide of vanadium is not fully oxidized, and the roasting time exceeds 300min, so that a large amount of cost loss is caused. After the roasting process is finished, the material is cooled along with the furnace or directly taken out; the crushed particle size of the roasted clinker is 250-300 meshes, and the particle size range is favorable for leaching vanadium.
The method as described above, preferably, in step S2, the leaching process is performed in a water bath or a heating jacket; in the leaching process, according to the liquid-solid ratio of deionized water to roasted clinker, the ratio of mL/g is 2-20: 1 adding deionized water into the leaching container, and adding roasted clinker when the temperature of the deionized water reaches 20-100 ℃. Because the roasted clinker is close to neutrality, the pH value of a leaching system is controlled to be 2-3 by adding an acid solution in the leaching process; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid; the acid is concentrated acid or diluted acid; the leaching temperature is 20-100 ℃; the liquid-solid ratio of the leaching system to the roasting clinker is 2-20 in mL/g: 1; the leaching process time is 30-180 min; and after leaching solid-liquid separation, repeatedly washing the filter cake with hot water with the pH of 2-3 and the temperature of 60-100 ℃.
The method as described above, preferably, in step S3, the vanadium precipitation process may be performed in a water bath or a heating jacket, and the vanadium precipitation additive is at least one of ammonium sulfate, ammonium carbonate, and ammonium bicarbonate; the addition amount of the vanadium precipitation additive is that the molar ratio of ammonium in the ammonium salt to vanadium in the leaching solution is 1.0-3.0; in the vanadium precipitation process, the pH value of the system is maintained to be 2-3 by adding an acid solution; the acid solution is at least one of sulfuric acid, hydrochloric acid and nitric acid; the acid is concentrated acid or diluted acid; the temperature is 60-100 ℃, and the vanadium precipitation time is 20-180 min; after the precipitate is completely separated from the solid, the filter cake is repeatedly washed by water. When the vanadium precipitation time is less than 20min, the vanadium precipitation rate is low, and when the vanadium precipitation time is more than 180min, the vanadium precipitation rate is not obviously increased, but a large amount of energy consumption is caused. Stirring is kept during the vanadium precipitation process. After vanadium precipitation, filtering and separating solid and liquid to obtain ammonium polyvanadate precipitation and manganese precipitation supernatant; after the precipitation is complete, the filter cake is repeatedly washed with water.
In the method, preferably, in step S4, the ammonium polyvanadate is dried at 80-120 ℃ for 5-24 h; the temperature during roasting is 500-600 ℃; the roasting time is 30-300 min.
This step can be carried out in a muffle furnace. Research shows that when the roasting temperature is lower than 500 ℃, ammonium polyvanadate can not be completely decomposed to generate vanadium pentoxide, so that the vanadium pentoxide has low purity, and when the roasting temperature is higher than 600 ℃, the vanadium pentoxide can be melted, and the product is not powdery.
The method as described above, preferably, in step S5, the carbonization is to add at least one of carbon dioxide gas, sodium carbonate solution and ammonium carbonate solution to the manganese-containing supernatant, wherein the carbon dioxide can be derived from carbon dioxide released during the roasting process of mixing the vanadium chromium slag and manganese carbonate or industrial carbon dioxide; in the carbonization process, the pH value of a carbonization system is maintained at 6-8 by adding an alkali solution; the alkali solution is at least one of sodium hydroxide solution, ammonia water, sodium carbonate and ammonium carbonate solution; the carbonization temperature is 20-100 ℃; the carbonization time is 10 min-120 min; the manganese carbonate precipitate obtained by filtration and separation is repeatedly washed with water.
In the method, preferably, in step S6, the manganese carbonate precipitate is dried before being returned to the roasting system, and the drying temperature is 80 ℃ to 120 ℃; the drying time is 5-24 h.
In the method, in step S7, the impurities removed by the vanadium precipitation waste liquid are mainly ammonia nitrogen. Wherein the ammonia nitrogen can be removed by biological method, ion exchange method, membrane separation method, chemical precipitation method, oxidation method, stripping method, etc.
Further, the method also comprises S8, and the vanadium extraction tailings are utilized: the leached slag containing chromium obtained in the step S2 is used for preparing ferrochromium alloy or further extracting chromium.
(III) advantageous effects
The invention has the beneficial effects that:
the method takes the vanadium-chromium slag as a raw material, converts vanadium into manganese vanadate dissolved in an acid solution through manganese roasting, and leaves chromium in a slag phase in the form of iron-chromium solid solution, so that the high-efficiency separation of vanadium and chromium is realized, and the defects of sodium roasting water leaching and calcification roasting acid leaching processes are effectively avoided.
Meanwhile, the process of the invention has three circulation routes:
(1) carbon dioxide gas released in the roasting process can be collected and used as a carbonizing agent for carbonizing and precipitating manganese from manganese-containing supernatant for recycling;
(2) the manganese carbonate which is a manganese precipitation product can be used as a roasting additive to return to a roasting system;
(3) the vanadium and manganese precipitation wastewater can be returned to leaching engineering as a leaching medium after impurity removal.
The three circulation routes realize the recycling of products and raw materials, effectively save the cost and reduce the emission of carbon dioxide greenhouse gas to a certain extent.
Compared with the existing industrialized sodium roasting and calcification process, the vanadium-chromium separation efficiency is higher; compared with the calcification roasting, the acid consumption in the leaching process is less, and the cost is effectively saved.
The method provided by the invention mainly adopts the method of manganese roasting, acid leaching vanadium and preparing vanadium pentoxide of the vanadium-chromium slag, realizes high-efficiency separation and extraction of vanadium and chromium in the high-chromium vanadium slag, and has high extraction rate. And the manganese in the leachate can be recovered in a carbonization mode and then used as a roasting additive to participate in the roasting process, so that the cost is greatly reduced. The obtained vanadium precipitation waste liquid can be recycled and returned to the leaching process for utilization after impurity removal, so that the recycling of the vanadium precipitation ammonia nitrogen waste water is realized, the water body pollution is avoided, and the production cost is effectively saved.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The invention adopts manganese carbonate and vanadium-chromium slag to mix and roast, wherein the manganese carbonate is used as a manganese additive to convert stable vanadium oxide manganese in the vanadium-chromium slag into acid-soluble manganese vanadate and transfer the acid-soluble manganese vanadate into a liquid phase in the acid leaching process. In the process, the closed cycle of the process is realized through three circulation routes, so that the cost is effectively saved and the environmental pollution is reduced. Compared with the sodium salt roasting process, the manganese carbonate roasting process has good vanadium-chromium separation effect, the waste water and the tailings for extracting vanadium and manganese have extremely little high-valence chromium, the pressure on the environment is very small, and the environment is protected and reaches the standard. Compared with the calcification roasting process, the vanadium-chromium separation efficiency is higher, no sulfate precipitate is generated in the leaching process, the vanadium-containing phase is not coated, the vanadium leaching rate is reduced, meanwhile, the sulfur content in the tailings is less, and if the vanadium extraction tailings are used for preparing the ferrochrome alloy, the sulfur content in the alloy reaches the standard.
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
A method for preparing vanadium pentoxide by using vanadium-chromium slag is disclosed, the process flow is shown in figure 1, and the method comprises the following steps:
(1) roasting: grinding and screening the vanadium-chromium slag, adding manganese carbonate into the obtained vanadium-chromium slag to mix the materials, and performing manganese roasting to obtain the vanadium-chromium slag with the granularity of 200-250 meshes so as to perform manganese oxide treatment on vanadium in the vanadium slag. Wherein the vanadium content (as V) of the vanadium-chromium slag2O5Calculated as Cr) is 14.42 percent, and the content of chromium (calculated as Cr)2O3Calculated by) is 9.45 percent, and is evenly mixed with manganese carbonate according to the mol ratio, and the vanadium in the vanadium-chromium slag is V2O3The molar ratio of the manganese to manganese in the manganese salt is 1: 2; roasting at 850 deg.C for 120min to obtain roasted clinker; crushing the roasted clinker to 250-300 meshes;
(2) leaching: the leaching process is carried out in a water bath kettle, deionized water is added into a leaching container according to the liquid-solid ratio of the deionized water to the roasted clinker of 5 mL/g, the roasted clinker is added at 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 90 min; after leaching, solid-liquid separation was carried out by filtration, and the filter cake was repeatedly washed with hot water having a pH of 2.5 and a temperature of 60 ℃. After leaching, the vanadium leaching rate is 90.26 percent and the chromium leaching rate is 0.15 percent by measuring the content of vanadium and chromium in the vanadium-containing leaching solution, thereby realizing the high-efficiency separation of vanadium and chromium.
(3) And (3) vanadium precipitation: the vanadium precipitation process is carried out in a water bath, and the vanadium precipitation additive is ammonium sulfate; the addition amount of the vanadium precipitation additive is that the molar ratio of ammonium in the ammonium salt to vanadium in the leaching solution is 1.5; in the vanadium precipitation process, the pH value of the system is maintained to be 2 by adding a sulfuric acid solution with the volume fraction of 10%; the vanadium precipitation temperature is 95 ℃, and the precipitation time is 60 min. After vanadium precipitation, filtering and separating solid and liquid to obtain ammonium polyvanadate precipitate and manganese-containing supernatant. After the vanadium precipitation, the vanadium precipitation rate is 99.52 percent by measuring the content of the vanadium in the vanadium precipitation supernatant.
(4) And (3) preparing a product: and (3) roasting the ammonium polyvanadate which is dried at 120 ℃ for 12 hours in advance at 550 ℃ for 120min to obtain the vanadium pentoxide with the purity of 99.95%.
(5) And (3) recovering manganese: introducing carbon dioxide into the manganese-containing supernatant, wherein the gas flow is 0.1L/min; during the carbonization process, the pH value of a carbonization system is maintained at about 6.8 by adding 10g/L of sodium hydroxide solution; the carbonization temperature is 40 ℃; the carbonization time is 60 min; filtering and separating solid and liquid to obtain manganese carbonate precipitate and vanadium extraction waste liquid.
(6) And (3) manganese circulation: and drying the manganese carbonate precipitate at 120 ℃ for 12h, and obtaining the manganese carbonate precipitate with 47% of manganese content and high purity (the manganese content of the manganese carbonate pure reagent is 47.8%) through chemical analysis. And (3) returning the precipitated manganese carbonate to the roasting system in the step (1) to participate in the next roasting process.
(7) Removing impurities: and (5) removing impurities in the vanadium extraction waste liquid obtained in the step (5) mainly by ammonia nitrogen. Wherein ammonia nitrogen is removed by a chemical precipitation method, and the ammonia nitrogen is used as a leaching medium in the step (2) after impurity removal and is recycled to the leaching system.
(8) And (3) utilization of vanadium extraction tailings: the chromium content in the vanadium extraction tailings is 11.68 percent, and the vanadium extraction tailings can be used as a raw material for preparing ferrochrome or extracting chromium.
Example 2
A method for preparing vanadium pentoxide by using vanadium-chromium slag comprises the following steps:
(1) roasting: grinding the vanadium-chromium slag, screening, adding rhodochrosite for mixing, and then performing manganese roasting, wherein the granularity of the vanadium-chromium slag is 250-300 meshes, so that the manganese oxide of vanadium in the vanadium slag can be conveniently realized. Wherein the vanadium content (as V) of the vanadium-chromium slag2O5Calculated as Cr) is 13.35 percent, and the content of chromium (calculated as Cr)2O3Calculated) is 8.77 percent, and is uniformly mixed with rhodochrosite, and the vanadium in the vanadium chromium slag is expressed as V according to the molar ratio2O3The molar ratio of manganese in the rhodochrosite to manganese is 1: 1; roasting at 800 ℃ for 300min to obtain roasted clinker; crushing the roasted clinker to 250-300 meshes;
(2) leaching: the leaching process is carried out in a water bath kettle, deionized water is added into a leaching container according to the liquid-solid ratio of the deionized water to the roasted clinker of 10 mL/g, the roasted clinker is added at the temperature of 80 ℃, and the pH value of a leaching system is controlled to be about 2.2 by adding 50% sulfuric acid by volume fraction; the leaching temperature is 80 ℃; adding and leaching the leaching system and the roasted clinker according to the liquid-solid ratio of mL/g of 10; the leaching process time is 120 min; after solid-liquid separation, the filter cake is repeatedly washed by hot water with the pH of 2.2 and the temperature of 80 ℃. After leaching, the vanadium leaching rate is 89.77 percent and the chromium leaching rate is 0.09 percent by measuring the content of vanadium and chromium in the vanadium-containing leaching solution, thereby realizing the high-efficiency separation of vanadium and chromium.
(3) And (3) vanadium precipitation: the vanadium precipitation process is carried out in a heating sleeve, and the vanadium precipitation additive is ammonium chloride; the addition amount of the vanadium precipitation additive is that the molar ratio of ammonium in the ammonium salt to vanadium in the leaching solution is 2; in the vanadium precipitation process, the pH value of the system is maintained to be 2.5 by adding a hydrochloric acid solution with the volume fraction of 20%; the vanadium precipitation temperature is 80 ℃, and the vanadium precipitation time is 120 min. After vanadium precipitation, filtering and separating solid and liquid to obtain ammonium polyvanadate precipitate and manganese-containing supernatant. After the vanadium precipitation, the vanadium precipitation rate is 98.78 percent by measuring the content of the vanadium in the vanadium precipitation supernatant.
(4) And (3) preparing a product: and (3) roasting ammonium polyvanadate which is dried at 100 ℃ for 24 hours in advance at 600 ℃ for 60 minutes to obtain vanadium pentoxide with the purity of 99.88%.
(5) And (3) recovering manganese: adding 200g/L sodium carbonate solution into the manganese-containing supernatant for carbonization; during the carbonization process, the pH value of a carbonization system is maintained at about 7.0 by adding 200g/L sodium carbonate solution; the carbonization temperature is 80 ℃; the carbonization time is 30 min; then filtering and separating solid and liquid to obtain manganese carbonate precipitate and vanadium extraction waste liquid.
(6) And (3) manganese circulation: and drying the manganese carbonate precipitate at 100 ℃ for 24h, and obtaining the manganese carbonate precipitate with 46.7% of manganese content and high purity (the manganese content of the manganese carbonate pure reagent is 47.8%) through chemical analysis. The precipitated manganese carbonate is returned to a roasting system to participate in the next roasting process.
(7) Removing impurities: and (5) removing impurities of the vanadium precipitation waste liquid mainly by ammonia nitrogen. Wherein the ammonia nitrogen is removed by an ion exchange method.
(8) And (3) utilization of vanadium extraction tailings: the chromium content in the vanadium extraction tailings is 11.73 percent, and the vanadium extraction tailings can be used as a raw material for preparing ferrochrome or extracting chromium.
Example 3
A method for preparing vanadium pentoxide by using vanadium-chromium slag comprises the following steps:
(1) roasting: grinding the vanadium-chromium slag, screening,adding manganese carbonate to mix, and then performing manganese roasting, wherein the granularity of the vanadium-chromium slag is 200-300 meshes, so that the manganese oxide of vanadium in the vanadium slag is conveniently formed. Wherein the vanadium content (as V) of the vanadium-chromium slag2O5Calculated as Cr) is 15.48 percent, and the content of chromium (calculated as Cr)2O3Calculated) is 6.55 percent, is evenly mixed with rhodochrosite according to the mol ratio, and the vanadium in the vanadium-chromium slag is V2O3The molar ratio of manganese in the rhodochrosite to manganese is 1: 3; roasting at 950 ℃ for 60min to obtain roasted clinker; crushing the roasted clinker to 200-300 meshes;
(2) leaching: the leaching process is carried out in a heating jacket, deionized water is added into a leaching container according to the liquid-solid ratio of the deionized water to the roasted clinker of 20 mL/g, the roasted clinker is added at 40 ℃, 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 40 ℃; the liquid-solid ratio of the leaching system to the roasted clinker is 20 in mL/g; the leaching process time is 60 min; after solid-liquid separation, the filter cake is repeatedly washed by hot water with the pH value of 2.8 and the temperature of 40 ℃. After leaching, the vanadium leaching rate is 88.54 percent and the chromium leaching rate is 0.23 percent by measuring the content of vanadium and chromium in the vanadium-containing leaching solution, thereby realizing the high-efficiency separation of vanadium and chromium.
(3) And (3) vanadium precipitation: the vanadium precipitation process is carried out in a heating sleeve, and a vanadium precipitation additive is added into the vanadium-containing leaching solution, wherein the vanadium precipitation additive is ammonium chloride; the addition amount of the vanadium precipitation additive is that the molar ratio of ammonium in the ammonium salt to vanadium in the leaching solution is 3; in the vanadium precipitation process, the pH value of the system is maintained to be 2 by adding a sulfuric acid solution with the volume fraction of 20%; the vanadium precipitation temperature is 100 ℃, and the precipitation time is 30 min. After vanadium precipitation, filtering and separating solid and liquid to obtain ammonium polyvanadate precipitate and manganese-containing supernatant. After the vanadium precipitation, the vanadium precipitation rate is 99.97 percent by measuring the content of the vanadium in the vanadium precipitation supernatant.
(4) And (3) preparing a product: and (3) roasting ammonium polyvanadate which is dried for 6 hours at 80 ℃ for 300min at 500 ℃ in advance to obtain vanadium pentoxide with the purity of 99.94%.
(5) And (3) recovering manganese: adding 300g/L ammonium carbonate solution into the manganese-containing supernatant for carbonization; during the carbonization process, the pH value of a carbonization system is maintained at about 8.0 by adding 300g/L of sodium carbonate solution; the carbonization temperature is 20 ℃; the carbonization time is 10 min; filtering and separating solid and liquid to obtain manganese carbonate precipitate and vanadium extraction waste liquid.
(6) And (3) manganese circulation: and drying the manganese carbonate precipitate at 80 ℃ for 6h, and obtaining the manganese carbonate precipitate with 46.1% of manganese content and high purity (the manganese content of the manganese carbonate pure reagent is 47.8%) through chemical analysis. The precipitated manganese carbonate is returned to a roasting system to participate in the next roasting process.
(7) Removing impurities: and (5) removing impurities of the vanadium precipitation waste liquid mainly by ammonia nitrogen. Wherein the ammonia nitrogen is removed by a chemical precipitation method.
(8) And (3) utilization of vanadium extraction tailings: the chromium content in the vanadium extraction tailings is 7.58 percent, and the vanadium extraction tailings can be used as a raw material for preparing ferrochrome or extracting chromium.
Comparative example 1
For vanadium content (in V)2O5Calculated as Cr) is 14.42 percent, and the content of chromium (calculated as Cr)2O3Calculated) 9.45 percent of vanadium-chromium slag is treated by conventional sodium salt roasting water leaching, the chromium-containing tailings and waste water are more, and the pollution to the environment is great; the content of sodium (by Na) in the vanadium extraction tailings2Calculated by O) is as high as 13.46 percent and cannot be utilized; the content of sodium in the leaching solution is higher, if the leaching solution is not subjected to impurity removal pretreatment, V2O5The purity of the product is only 91.49%.
Comparative example 2
For vanadium content (in V)2O5Calculated as Cr) is 14.42 percent, and the content of chromium (calculated as Cr)2O3Calculated) 9.45 percent of vanadium-chromium slag is subjected to conventional calcification roasting acid leaching treatment, the vanadium-chromium leaching rates are 87.74 percent and 0.68 percent respectively, the vanadium leaching rate is lower than that of the vanadium leaching rate of the invention, and the chromium leaching rate is higher than that of the invention. The vanadium-chromium separation efficiency is inferior to that of the present invention. The sulfur content of the vanadium extraction tailings is higher than 1.3 percent, so that the sulfur content of the smelted alloy does not reach the standard.
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 are within the protection scope of the technical solution of the present invention.
Claims (6)
1. A method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate is characterized by comprising the following steps:
s1, roasting: mixing the vanadium-chromium slag and manganese carbonate to obtain a mixed material, and roasting the mixed material at a high temperature to obtain a roasted clinker;
s2, leaching: leaching the roasted clinker obtained in the step S1, and then filtering to obtain vanadium-containing leaching liquid and chromium-containing leaching slag;
s3, precipitating vanadium: adding a vanadium precipitation additive into the vanadium-containing leaching solution obtained in the step S2, adjusting the pH value to 2-3, precipitating vanadium, and filtering to obtain an ammonium polyvanadate precipitate and a manganese-containing supernatant;
s4, preparing a product: roasting the ammonium polyvanadate precipitate obtained in the step S3 to obtain a vanadium pentoxide product;
s5, recovering manganese: carbonizing the manganese-containing supernatant obtained in the step S3, and then filtering to obtain manganese carbonate precipitate and vanadium extraction waste liquid;
s6, manganese cycle: the manganese carbonate precipitate is recycled to the roasting system to be used as an additive to participate in the next roasting;
s7, recycling vanadium extraction waste liquid: after the impurities of the vanadium extraction waste liquid obtained in the step S5 are removed, the vanadium extraction waste liquid is used as a leaching medium in the step S2 to be recycled to a leaching system;
in step S1, the vanadium content in the vanadium-chromium slag is V2O55-20% of chromium, and the chromium content is Cr2O3The content of the vanadium chromium slag is 5-15%, the particle size of the vanadium chromium slag is 200-300 meshes, and the manganese carbonate is at least one of a manganese carbonate reagent or rhodochrosite; the dosage ratio of the vanadium chromium slag to the manganese carbonate is V in terms of vanadium in the vanadium chromium slag2O3The molar ratio of manganese to manganese in manganese carbonate is 1: 0.5 to 3; in step S1, the high-temperature roasting temperature is 800-950 ℃, the time is 60-300 min, and the heating rate is 2-10 ℃/min;
in step S2, the process of leaching is performed in a water bath or heating jacket; according to the liquid-solid ratio of deionized water to roasted clinker, the ratio of mL/g is 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 and nitric acid; the acid is concentrated acid or diluted acid; the leaching temperature is 20-100 ℃; the leaching process time is 30-180 min; after leaching and solid-liquid separation, repeatedly washing a filter cake by using hot water with the pH of 2-3 and the temperature of 60-100 ℃;
in step S5, the carbonization is at least one of carbon dioxide gas, sodium carbonate solution and ammonium carbonate solution added in the manganese-containing supernatant, wherein the carbon dioxide is derived from carbon dioxide released in the roasting process of mixing the vanadium chromium slag and the manganese carbonate or industrial carbon dioxide; in the carbonization process, the pH value of a carbonization system is maintained at 6-8 by adding an alkali solution; the alkali solution is at least one of sodium hydroxide solution, ammonia water, sodium carbonate and ammonium carbonate solution; the carbonization temperature is 20-100 ℃; the carbonization time is 10 min-120 min; the manganese carbonate precipitate obtained by filtration and separation is repeatedly washed with water.
2. The method of claim 1, wherein in step S3, the vanadium precipitation additive is at least one of ammonium sulfate, ammonium carbonate, ammonium bicarbonate; the addition amount of the vanadium precipitation additive is that the molar ratio of ammonium in the ammonium salt to vanadium in the leaching solution is 1.0-3.0; in the vanadium precipitation process, the pH value of the system is maintained to be 2-3 by adding acid; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid; the temperature is 60-100 ℃, and the vanadium precipitation time is 20-180 min; after the precipitate is completely separated from the solid, the filter cake is repeatedly washed by water.
3. The method of claim 1, wherein in step S4, the ammonium polyvanadate is dried at 80 ℃ to 120 ℃ in advance; the drying time is 5-24 h; the roasting temperature is 500-600 ℃; the roasting time is 30-300 min.
4. The method of claim 1, wherein in step S6, the manganese carbonate precipitate is dried before being returned to the roasting system, the drying temperature being 80 ℃ to 120 ℃; the drying time is 5-24 h.
5. The method of claim 1, wherein in step S7, the impurity removed from the vanadium precipitation waste liquid is ammonia nitrogen.
6. The method of any one of claims 1-5, further comprising
S8, utilizing the vanadium extraction tailings: the leached slag containing chromium obtained in the step S2 is used for preparing ferrochromium alloy or further extracting chromium.
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| CN111392774B (en) * | 2020-03-13 | 2022-09-02 | 吉林吉恩镍业股份有限公司 | Method for producing ammonium polyvanadate and high-heat-energy carbon powder by using vanadium-containing carbon ash as raw material |
| CN112111661B (en) * | 2020-09-24 | 2022-07-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting vanadium by calcium-manganese composite roasting of vanadium slag |
| CN112708757B (en) * | 2020-11-27 | 2023-11-14 | 核工业北京化工冶金研究院 | Method for recycling uranium and vanadium precipitation mother liquor |
| CN112430740B (en) * | 2020-11-30 | 2022-05-10 | 东北大学 | Method for strengthening vanadium-chromium separation by cooperatively roasting vanadium slag through calcium salt and manganese salt |
| CN113582244A (en) * | 2021-06-29 | 2021-11-02 | 南通金通储能动力新材料有限公司 | Method for reducing sodium content in high-sodium nickel cobalt manganese hydroxide |
| CN113957262B (en) * | 2021-10-29 | 2022-09-23 | 东北大学 | Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium |
| CN114349243A (en) * | 2021-11-29 | 2022-04-15 | 攀钢集团研究院有限公司 | Treatment method of vanadium precipitation wastewater of calcification vanadium extraction process |
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