CN107954474B - Method for producing vanadium product and basic chromium sulfate by using vanadium-chromium solution - Google Patents
Method for producing vanadium product and basic chromium sulfate by using vanadium-chromium solution Download PDFInfo
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- CN107954474B CN107954474B CN201810002197.0A CN201810002197A CN107954474B CN 107954474 B CN107954474 B CN 107954474B CN 201810002197 A CN201810002197 A CN 201810002197A CN 107954474 B CN107954474 B CN 107954474B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G37/00—Compounds of chromium
- C01G37/08—Chromium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a method for producing vanadium products and basic chromium sulfate by using a vanadium-chromium solution, which comprises the steps of hydrolyzing and precipitating vanadium, carrying out calcification reaction, enriching chromium, preparing basic chromium sulfate and the like to obtain high-purity vanadium products and basic chromium sulfate products, wherein the purity of the obtained vanadium products can reach more than 99.5 percent, and Cr in the basic chromium sulfate2O3The content can reach 24-26%, the content of impurity Fe is less than 0.1%, the recovery rate of vanadium and chromium can reach more than 99.5%, and the purpose of efficiently extracting and separating vanadium and chromium is realized. The production process is clean, the brine and the NaOH mother liquor generated in the preparation process can be returned to a system for use, and no ammonia nitrogen wastewater is generated in the whole process flow. The invention has the advantages of feasible technology, simple equipment, low production cost, easy realization of automation, and good economic benefit and application prospect.
Description
Technical Field
The invention belongs to the technical field of vanadium chemical metallurgy, and particularly relates to a method for cleanly producing a vanadium product and basic chromium sulfate by using a vanadium-chromium solution.
Background
Vanadium and chromium are important strategic resources and, due to similar properties, are often present in a symbiotic manner in vanadium chromite magnetite. The vanadium-chromium magnetite ore is subjected to blast furnace smelting, converter vanadium extraction and other processes to obtain chromium-containing vanadium slag. The vanadium extraction by sodium salt roasting of vanadium slag is a mainstream vanadium extraction process adopted in vanadium production at home and abroad, vanadium slag is subjected to sodium salt roasting, leaching, solution purification and other steps to obtain vanadium-chromium solution systems with different concentrations, and because the properties of the aqueous solutions of vanadium and chromium are similar, how to efficiently and cleanly extract vanadium and chromium from the aqueous solutions, and meanwhile, how to avoid the formation of dangerous waste and a heavy pollution source by vanadium extraction tailings is an important direction for the development of vanadium enterprises and is also the key point of current research.
Aiming at a vanadium-chromium-containing solution obtained by chemically converting (roasting, solvent leaching and the like) vanadium-chromium-containing minerals (such as vanadium slag), the existing vanadium-chromium separation method mainly comprises the following steps: extraction, chemical precipitation, ion exchange, crystallization, and electrochemical methods.
CN102531056A discloses a method for cleanly producing sodium vanadate and sodium chromate by pressure leaching of vanadium slag, which comprises the following steps: (1) preparing materials: mixing vanadium slag and NaOH solution to obtain a reaction material; (2) reaction: vanadium slag and oxidizing gas are subjected to oxidation reaction in NaOH solution under high pressure to obtain vanadium slag containing NaOH and Na3VO4、Na2CrO4And a solution of water-soluble impurity components and a solid-liquid mixed slurry of iron-rich tailings; (3) solid-liquid separation; (4) adding a desiliconization agent to remove impurities; (5) crystallizing sodium vanadate; (6) crystallizing sodium chromate. The method is easy to operate and has good safety; the operation temperature is greatly lower than the temperature of the traditional vanadium extraction process, the energy consumption is low, the high-efficiency co-extraction of vanadium and chromium is realized, and the extraction rate of vanadium and chromium is higher than 95 percent. However, the following problems also exist: (1) because high pressure and strong alkali are used, the requirement on equipment materials is high; (2) the impurity elements in the circulating mother liquor are continuously enriched, which affects the product quality and needs impurity removal procedures.
CN104556522 discloses a method for separating vanadium and chromium from a mixed solution of vanadium and chromium, comprising the following steps: A. adjusting the pH value of the mixed solution to 3.0-4.0, and adsorbing vanadium and chromium in the mixed solution by an ion exchange resin adsorption method to obtain vanadium and chromium containing resin; B. eluting the vanadium-chromium-containing resin by using 3-4% sulfuric acid-ethanol solution to obtain vanadium-containing resin and chromium-containing solution; C. desorbing the vanadium-containing resin to obtain vanadium-containing desorption solution, and performing vanadium precipitation treatment on the vanadium-containing desorption solution to obtain vanadate; D. calcining vanadate to obtain vanadium pentoxide; E. the chromium-containing solution is adjusted in pH for neutralization, chromium precipitates as a hydrate Cr (OH)3·nH2Separating out the O form, and calcining to prepare the chromium sesquioxide. The process flow is simple, easy to operate and low in cost, and is beneficial to separating and recycling vanadium and chromium resources, but the ion exchange resin is used, so that the one-time investment is large, the operating conditions are harsh, the resin is easy to be poisoned to influence the exchange efficiency, and the resin needs to be replaced in time.
CN103966438A provides a method for electrolytically separating vanadium and chromium from a vanadium-chromium containing solution, which comprises: adjusting the pH value of the vanadium-chromium-containing solution to 0-1.0; placing the solution containing vanadium and chromium into an electrolytic cell for electrolysis, wherein the electrolytic cell is divided into a cathode chamber and an anode chamber by an ion exchange membrane; and after the vanadium and the chromium in the vanadium-chromium-containing solution are electrolyzed and migrated, removing the anolyte in the anode chamber from the anode chamber, and removing the catholyte in the cathode chamber from the cathode chamber to complete the separation of the vanadium and the chromium in the vanadium-chromium-containing solution. Although the method adopts an electrochemical method to realize the direct separation of vanadium and chromium in the vanadium-chromium solution, the energy consumption in the electrolysis process is too much, the vanadium-chromium separation rate is still too low, and the purity of the obtained product is insufficient.
Although the method can effectively extract vanadium and chromium, the method generally has the problems of high equipment requirement, easy accumulation of impurity elements, harsh operating conditions, high energy consumption, insufficient product purity and the like. Therefore, there is a need to provide a new method for extracting and separating vanadium and chromium by using a vanadium-chromium solution in a clean and efficient way through an improved process.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for cleanly producing a vanadium product and basic chromium sulfate by using a vanadium-chromium solution, wherein the vanadium product and the basic chromium sulfate are obtained by the steps of hydrolyzing and precipitating vanadium, carrying out calcification reaction, enriching chromium, preparing basic chromium sulfate and the like, the purity of the vanadium product can reach more than 99.5 percent, and Cr in the basic chromium sulfate is more than or equal to that of the basic chromium sulfate2O3The content can reach 24-26%, the Fe content is less than 0.1%, and the recovery rate of vanadium and chromium reaches more than 99.5%; the brine and the NaOH mother liquor generated in the preparation process can be returned to the system for reuse, ammonia nitrogen wastewater is not generated in the whole process flow, the aim of clean production is achieved, and the method has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for producing a vanadium product and basic chromium sulfate by using a vanadium-chromium solution, which comprises the following steps:
(1) adjusting the pH value of the vanadium-chromium solution to carry out hydrolysis vanadium precipitation, and then carrying out solid-liquid separation to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) mixing the red cake obtained in the step (1) with a calcification agent, adding the mixture into water for calcification reaction, and performing solid-liquid separation after the reaction is finished to obtain solid-phase calcium vanadate;
(3) performing secondary vanadium precipitation and chromium reduction precipitation on the vanadium-precipitated liquid obtained in the step (1) to obtain a chromium-containing material and a sodium salt solution;
(4) and (3) adding the chromium-containing material obtained in the step (3) into sulfuric acid to perform acid dissolution reaction, adding an oxidant after the reaction is finished, then adjusting the pH, performing solid-liquid separation to obtain a chromium sulfate solution, then adjusting the basicity, and evaporating and drying to obtain basic chromium sulfate.
The vanadium-chromium solution in the step (1) is a solution containing vanadium and chromium elements, and is preferably a vanadium extraction purification solution obtained by a vanadium slag sodium salt roasting vanadium extraction process.
According to the invention, the pH value during the hydrolysis vanadium precipitation in step (1) is adjusted to 1.6-1.9, which may be 1.6, 1.7, 1.8 or 1.9, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the invention, the pH is adjusted in step (1) with hydrochloric acid.
According to the invention, the calcification agent in step (2) is calcium oxide.
According to the invention, the addition of the calcification agent in step (2) according to a molar ratio Ca/V (1-3):1, which may be, for example, 1:1, 3:2, 2:1, 5:2 or 3:1, and the particular values between the above values, which are limited to space and for the sake of brevity, are not exhaustive.
According to the present invention, the calcification reaction temperature in step (2) is 50-100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the present invention is not exhaustive.
According to the invention, the calcification reaction time in step (2) is 0.2-2h, for example, 0.2h, 0.4h, 0.6h, 0.8h, 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, and the specific values therebetween, which are not exhaustive for reasons of space and brevity.
After the calcium vanadate is obtained in the step (2), the calcium vanadate can be used as a raw material to prepare a vanadium product by a conventional method in the field, for example, the obtained calcium vanadate can be subjected to ammonification, dissolution, impurity removal, crystallization and calcination to prepare vanadium pentoxide, but the method is not limited to this. The operation of preparing vanadium pentoxide by using calcium vanadate is a conventional operation in the field, and the specific conditions are not particularly limited in the invention.
According to the invention, the vanadium precipitation agent used for secondary vanadium precipitation in the step (3) is polyferric chloride, and polyferric sulfate is not used for avoiding introducing new impurities.
The secondary vanadium precipitation and the reduction chromium precipitation in step (3) of the present invention are conventional operations in the art, and the present invention is not particularly limited to specific conditions, and the following operations may be performed as an example, but not limited thereto.
The secondary vanadium precipitation and chromium reduction precipitation operations can be as follows: adding a vanadium precipitation agent into the vanadium precipitation solution obtained in the step (1) to adjust the pH value to 4.5-5.5 for secondary vanadium precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain secondary vanadium precipitation solution; and adding a reducing agent into the obtained secondary vanadium precipitation solution to perform chromium reduction reaction, then adjusting the pH value to 6.8-7.2, and performing solid-liquid separation to obtain a chromium-containing material and a sodium salt solution.
The reducing agent is a reducing agent commonly used in the art, and may be, for example, sulfur dioxide, sodium sulfite, sodium thiosulfate, or the like, but is not limited thereto, and any reducing agent that can achieve reduction of chromium is suitable for use in the present invention.
After the completion of the chromium reduction reaction, Cr (OH) is formed by adjusting pH3Precipitating chromium, wherein the pH value of trivalent chromium beginning to precipitate is 4.6, and Cr (OH) can be realized at pH of 6.8-7.23And completely precipitating. After solid-liquid separationThe obtained liquid phase contains high-concentration sodium salt, and the obtained brine can return to the sodium salt roasting and leaching process.
The chromium-containing material obtained in the step (3) of the invention has high chromium content and is a chromium-rich material.
According to the invention, the concentration of the sulfuric acid used in step (4) is 10 to 98 wt.%, and may be, for example, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.% or 98 wt.%, and the particular values between the above values, are not exhaustive for reasons of space and simplicity.
According to the invention, the ratio of the sulfuric acid to the chromium-containing material in step (4) is (2-8):1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 or 8:1, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
The unit of the liquid-solid ratio is ml: g.
According to the present invention, the temperature of the acid dissolution reaction in the step (4) is 30-90 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the specific values therebetween are limited to space and for brevity, and the present invention is not exhaustive.
According to the invention, the acid dissolution reaction time in the step (4) is 0.5-2h, for example, 0.5h, 0.8h, 1.0h, 1.3h, 1.5h, 1.8h or 2h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the oxidant in the step (4) is any one or combination of at least two of air, ozone or hydrogen peroxide; for example, it may be any one of air, ozone or hydrogen peroxide, with a typical but non-limiting combination of: air and ozone; air and hydrogen peroxide; ozone and hydrogen peroxide; air, ozone and hydrogen peroxide.
Because the reducing agent is introduced in the step (3) to reduce part of ferric iron in the solution into ferrous iron, and the ferrous iron has high solubility in an acidic solution and is not easy to remove, the invention selects to add the oxidizing agent in the step (4) to oxidize the ferrous iron in the solution into ferric iron.
According to the invention, an acid-base regulator is added in the step (4) to regulate the pH, and the acid-base regulator is sulfuric acid, NaOH or Na2CO3Any one of them.
According to the invention, the pH of the pH adjusted to 2 to 4.6 after the addition of the oxidizing agent in step (4), which may be, for example, 2, 2.3, 2.5, 2.8, 3, 3.3, 3.5, 3.8, 4, 4.3 or 4.6, and the values between these values, are not exhaustive for reasons of space and simplicity.
After the acid dissolution reaction in the step (4) is finished, oxidizing agent is added to oxidize ferrous iron into ferric iron, and then acid-base regulator is added to regulate pH value for iron removal. The pH value when ferric iron begins to precipitate is 2, and the pH value when trivalent chromium begins to precipitate is 4.6, so the pH value is controlled to be between 2 and 4.6, so that chromium does not precipitate while iron in the solution precipitates, and further the removal of iron in the chromium sulfate solution is realized.
In the invention, the acid-base regulator is added in the step (4) to remove iron, and then the iron oxide red (the main component is ferric oxide) is obtained through solid-liquid separation, and the obtained iron oxide red can be returned to the step (3) to be used as a vanadium precipitation agent after being dissolved by acid. Because a small amount of chromium element is mixed in the iron oxide red, the iron oxide red cannot be used as an iron oxide red pigment; but after the iron oxide is dissolved by hydrochloric acid, the iron oxide can be prepared and further returned to the step (3) to be used as a vanadium precipitation agent, and meanwhile, the chromium element in the iron oxide red is also returned to the preparation system.
According to the invention, NaOH is added in step (4) to adjust the basicity.
According to the invention, the basicity adjusted in step (4) is 32-36%, preferably 33%, and may be, for example, 32%, 33%, 34%, 35% or 36%, and the specific values between the above values, which are limited to space and for the sake of brevity, are not exhaustive.
The solid-liquid separation is carried out by the conventional operation in the field, such as filtration, suction filtration, centrifugation, etc., but the invention is not limited thereto, and the adjustment should be carried out in practical situations. In the present invention, solid-liquid separation is preferably performed by filtration.
As a preferred technical scheme, the method comprises the following steps:
(1) regulating the pH value of the vanadium-chromium solution to 1.6-1.9 by using hydrochloric acid to carry out hydrolysis vanadium precipitation, and then carrying out solid-liquid separation to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V (1-3) to 1, adding the mixture into water, controlling the temperature to be 50-100 ℃ to carry out calcification reaction, carrying out solid-liquid separation after the reaction is carried out for 0.2-2h to obtain solid-phase calcium vanadate; carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) adding polyferric chloride into the vanadium-precipitated liquid obtained in the step (1) to carry out secondary vanadium precipitation, then carrying out reduction chromium precipitation, and carrying out solid-liquid separation after the reaction is finished to obtain a chromium-containing material and brine; the obtained brine can return to the sodium salt roasting and leaching working procedures;
(4) adding the chromium-containing material obtained in the step (3) into sulfuric acid with the concentration of 10-98 wt% according to the liquid-solid ratio of (2-8):1, controlling the temperature to be 30-90 ℃ to carry out acid dissolution reaction for 0.5-2h, adding an oxidant after the reaction is finished, then adding an acid-base regulator to regulate the pH to be 2-4.6, carrying out solid-liquid separation to obtain a chromium sulfate solution, then adding NaOH to regulate the basicity to be 32-36%, and then evaporating and drying to obtain basic chromium sulfate; the oxidant air, ozone or hydrogen peroxide is any one or the combination of at least two of the oxidant air, ozone and hydrogen peroxide, and the acid-base regulator is sulfuric acid, NaOH or Na2CO3Any one of them.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention prepares two products of high-purity vanadium and basic chromium sulfate by using the vanadium-chromium solution simultaneously, the purity of the vanadium product can reach more than 99.5 percent, and Cr in the basic chromium sulfate2O3The content can reach 24-26%, and the Fe content in the basic chromium sulfate product is less than 0.1%.
(2) The method provided by the invention can efficiently recover valuable elements in the vanadium-chromium solution, and the recovery rate of vanadium and chromium reaches more than 99.5%; and the brine and the NaOH mother liquor generated in the preparation process can be returned to the system for use, no ammonia nitrogen wastewater is generated in the whole process, and the aim of clean production is fulfilled.
(3) The invention has the advantages of feasible technology, simple equipment, low production cost, easy realization of automation and good application prospect.
Drawings
FIG. 1 is a process flow diagram provided by one embodiment of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
As shown in fig. 1, a process flow for producing a vanadium product and basic chromium sulfate by using a vanadium-chromium solution according to a specific embodiment of the present invention may be: using vanadium-chromium solution obtained by carrying out sodium roasting, clinker leaching, filtering and washing, impurity removal and other conventional steps on vanadium slag and sodium salt as raw materials, carrying out hydrolysis vanadium precipitation by adjusting pH, and then carrying out solid-liquid separation to obtain solid-phase red cake and vanadium-chromium-containing vanadium-precipitation solution; mixing the obtained red cake and calcium oxide, adding the mixture into water for calcification reaction, and performing solid-liquid separation after the reaction is finished, wherein the obtained liquid phase is NaOH solution and can be used for leaching reaction of the roasted clinker; carrying out conventional operations such as ammonification, dissolution, impurity removal, crystallization, calcination and the like on the obtained solid-phase calcium vanadate to obtain high-purity vanadium pentoxide (the purity is more than 99.5%); adding a vanadium precipitation agent into the obtained vanadium precipitation solution, adjusting the pH value by using NaOH to perform secondary vanadium precipitation reaction, and performing solid-liquid separation to obtain solid-phase iron vanadate mud and secondary vanadium precipitation solution; the obtained ferric vanadate mud can be used as a vanadium source and returned to the sodium salt roasting step for vanadium extraction; adding a reducing agent into the obtained secondary vanadium precipitation solution to carry out chromium reduction reaction for chromium precipitation, and carrying out solid-liquid separation after the reaction is finished to obtain a chromium-containing material (chromium-rich material) and a sodium salt solution; the obtained sodium salt solution can be used as a sodium source to return to the sodium roasting and leaching step for vanadium extraction; adding sulfuric acid into a chromium-containing material for acid dissolution reaction, adding an oxidant and an acid-base regulator after the reaction is finished, adjusting the pH value for iron removal, performing solid-liquid separation to obtain a chromium sulfate solution and iron red slag, and performing acid dissolution on the obtained iron red slag to obtain a vanadium precipitation agent for secondary vanadium extraction; NaOH is added to adjust the basicity of the chromium sulfate solution, and then the basic chromium sulfate product is obtained after evaporation and drying.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
(1) Hydrolyzing and precipitating vanadium: adding hydrochloric acid into a vanadium-chromium solution containing 24.5g/L vanadium and 568.2mg/L chromium to adjust the pH value to 1.8, hydrolyzing to precipitate vanadium, and filtering to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) calcification reaction: mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V of 1.5, adding the mixture into water for calcification reaction, controlling the reaction temperature to be 95 ℃, reacting for 1h, filtering to obtain solid-phase calcium vanadate, and carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) enrichment of chromium: adding polyferric chloride into the vanadium-precipitated solution obtained in the step (1), adjusting the pH value to 5 to carry out secondary vanadium precipitation reaction, filtering after the reaction is finished, introducing sulfur dioxide into the obtained filtrate to carry out chromium reduction reaction, adjusting the pH value to 7, and filtering to obtain a chromium-containing material and a sodium salt solution;
(4) preparing basic chromium sulfate: adding the chromium-containing material obtained in the step (3) into a sulfuric acid solution with the concentration of 98 wt% according to the liquid-solid ratio of 3:1 for acid dissolution, controlling the reaction temperature to be 90 ℃, adding hydrogen peroxide for oxidation after the reaction is finished, then adjusting the pH value to be 4 for iron removal, filtering to obtain a chromium sulfate solution, adding NaOH into the solution to adjust the basicity to be 33%, and evaporating and drying to obtain a basic chromium sulfate product.
Through detection, in the embodiment, the hydrolysis vanadium precipitation rate is 95.9%, the purity of the obtained vanadium pentoxide is 99.52%, and the Cr in the obtained basic chromium sulfate2O3The content is 24.6 percent and the Fe content is 0.05 percent.
Example 2
(1) Hydrolyzing and precipitating vanadium: adding hydrochloric acid into a vanadium-chromium solution containing 24.5g/L vanadium and 568.2mg/L chromium to adjust the pH value to 1.9, hydrolyzing to precipitate vanadium, and filtering to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) calcification reaction: mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V of 1.9, adding the mixture into water for calcification reaction, controlling the reaction temperature to be 85 ℃ and the reaction time to be 1.5h, filtering to obtain solid-phase calcium vanadate, and carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) enrichment of chromium: adding polyferric chloride into the vanadium-precipitated solution obtained in the step (1), adjusting the pH value to 4.5 to perform a secondary vanadium precipitation reaction, filtering after the reaction is finished, adding sodium thiosulfate into the obtained filtrate to perform a chromium reduction reaction, adjusting the pH value to 7.1, and filtering to obtain a chromium-containing material and a sodium salt solution;
(4) preparing basic chromium sulfate: adding the chromium-containing material obtained in the step (3) into a sulfuric acid solution with the concentration of 50 wt% according to the liquid-solid ratio of 6:1 for acid dissolution, controlling the reaction temperature to be 80 ℃, adding hydrogen peroxide for oxidation after the reaction is finished, then adjusting the pH value to be 3.5 for iron removal, filtering to obtain a chromium sulfate solution, adding NaOH into the solution to adjust the basicity to be 33%, and evaporating and drying to obtain a basic chromium sulfate product.
Through detection, in the embodiment, the hydrolysis vanadium precipitation rate is 96.3%, the purity of the obtained vanadium pentoxide is 99.51%, and the Cr in the obtained basic chromium sulfate2O3The content is 24.3 percent and the Fe content is 0.08 percent.
Example 3
(1) Hydrolyzing and precipitating vanadium: adding hydrochloric acid into a vanadium-chromium solution containing 24.5g/L vanadium and 568.2mg/L chromium to adjust the pH value to 1.6, hydrolyzing to precipitate vanadium, and filtering to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) calcification reaction: mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V of 1.3, adding the mixture into water for calcification reaction, controlling the reaction temperature to be 75 ℃ and the reaction time to be 2h, filtering to obtain solid-phase calcium vanadate, and carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) enrichment of chromium: adding polyferric chloride into the vanadium-precipitated liquid obtained in the step (1), adjusting the pH value to 5.2 to carry out secondary vanadium precipitation reaction, filtering after the reaction is finished, adding sodium sulfite into the obtained filtrate to carry out chromium reduction reaction, adjusting the pH value to 7, and filtering to obtain a chromium-containing material and a sodium salt solution;
(4) preparing basic chromium sulfate: adding the chromium-containing material obtained in the step (3) into a sulfuric acid solution with the concentration of 30 wt% according to the liquid-solid ratio of 8:1 for acid dissolution, controlling the reaction temperature to be 60 ℃, adding hydrogen peroxide for oxidation after the reaction is finished, then adjusting the pH to be 4.5 for iron removal, filtering to obtain a chromium sulfate solution, adding NaOH into the solution to adjust the basicity to be 34%, and evaporating and drying to obtain a basic chromium sulfate product.
Through detection, in the embodiment, the hydrolysis vanadium precipitation rate is 96.1%, the purity of the obtained vanadium pentoxide is 99.56%, and the Cr in the obtained basic chromium sulfate2O3The content is 24.9 percent and the Fe content is 0.04 percent.
Example 4
(1) Hydrolyzing and precipitating vanadium: adding hydrochloric acid into a vanadium-chromium solution containing 24.5g/L vanadium and 568.2mg/L chromium to adjust the pH value to 1.7, hydrolyzing to precipitate vanadium, and filtering to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) calcification reaction: mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V of 2.2, adding the mixture into water for calcification reaction, controlling the reaction temperature to be 60 ℃ and the reaction time to be 1.5h, filtering to obtain solid-phase calcium vanadate, and carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) enrichment of chromium: adding polyferric chloride into the vanadium-precipitated solution obtained in the step (1), adjusting the pH value to 4.8 to perform a secondary vanadium precipitation reaction, filtering after the reaction is finished, introducing sulfur dioxide into the obtained filtrate to perform a chromium reduction reaction, adjusting the pH value to 7, and filtering to obtain a chromium-containing material and a sodium salt solution;
(4) preparing basic chromium sulfate: adding the chromium-containing material obtained in the step (3) into a sulfuric acid solution with the concentration of 40 wt% according to the liquid-solid ratio of 7:1 for acid dissolution, controlling the reaction temperature to be 70 ℃, introducing ozone for oxidation after the reaction is finished, then adjusting the pH value to be 4 for iron removal, filtering to obtain a chromium sulfate solution, adding NaOH into the solution to adjust the basicity to be 33%, and evaporating and drying to obtain a basic chromium sulfate product.
Through detection, in the embodiment, the hydrolysis vanadium precipitation rate is 96.5%, the purity of the obtained vanadium pentoxide is 99.52%, and the Cr in the obtained basic chromium sulfate2O3The content is 24.5 percent and the Fe content is 0.06 percent.
Example 5
(1) Hydrolyzing and precipitating vanadium: adding hydrochloric acid into a vanadium-chromium solution containing 24.5g/L vanadium and 568.2mg/L chromium to adjust the pH value to 1.7, hydrolyzing to precipitate vanadium, and filtering to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) calcification reaction: mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V of 3, adding the mixture into water for calcification reaction, controlling the reaction temperature to be 50 ℃ and the reaction time to be 1h, filtering to obtain solid-phase calcium vanadate, and carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) enrichment of chromium: adding polyferric chloride into the vanadium-precipitated solution obtained in the step (1), adjusting the pH value to 5 to carry out secondary vanadium precipitation reaction, filtering after the reaction is finished, introducing sulfur dioxide into the obtained filtrate to carry out chromium reduction reaction, adjusting the pH value to 6.9, and filtering to obtain a chromium-containing material and a sodium salt solution;
(4) preparing basic chromium sulfate: adding the chromium-containing material obtained in the step (3) into a sulfuric acid solution with the concentration of 60 wt% according to the liquid-solid ratio of 4:1 for acid dissolution, controlling the reaction temperature to be 50 ℃, introducing air for oxidation after the reaction is finished, then adjusting the pH value to be 3 for iron removal, filtering to obtain a chromium sulfate solution, adding NaOH into the solution to adjust the basicity to be 33%, and evaporating and drying to obtain a basic chromium sulfate product.
Through detection, in the embodiment, the hydrolysis vanadium precipitation rate is 95.5%, the purity of the obtained vanadium pentoxide is 99.58%, and the Cr in the obtained basic chromium sulfate2O3The content is 24.8 percent and the Fe content is 0.09 percent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
1. A method for producing a vanadium product and basic chromium sulfate by using a vanadium-chromium solution is characterized by comprising the following steps:
(1) adjusting the pH value of the vanadium-chromium solution to carry out hydrolysis vanadium precipitation, and then carrying out solid-liquid separation to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) mixing the red cake obtained in the step (1) with a calcification agent, adding the mixture into water for calcification reaction, and performing solid-liquid separation after the reaction is finished to obtain solid-phase calcium vanadate;
(3) adding polyferric chloride into the vanadium precipitation solution obtained in the step (1) to adjust the pH value to 4.5-5.5 for secondary vanadium precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain secondary vanadium precipitation solution; adding a reducing agent into the obtained secondary vanadium precipitation solution to carry out chromium reduction reaction, then adjusting the pH value to 6.8-7.2, and carrying out solid-liquid separation to obtain a chromium-containing material and a sodium salt solution;
(4) adding the chromium-containing material obtained in the step (3) into sulfuric acid to perform acid dissolution reaction, adding an oxidant after the reaction is finished, then adjusting the pH to 2-4.6, performing solid-liquid separation to obtain solid-phase iron red and a chromium sulfate solution, adding NaOH into the chromium sulfate solution to adjust the basicity to be 32-36%, and evaporating and drying to obtain basic chromium sulfate; the iron oxide red can be returned to the step (3) to be used as a vanadium precipitation agent after being dissolved by acid;
and (4) returning the sodium salt solution obtained by solid-liquid separation in the step (3) to the sodium salt roasting and leaching process.
2. The method of claim 1, wherein the pH is adjusted to 1.6-1.9 during the hydrolysis vanadium precipitation in step (1).
3. The method of claim 1, wherein the pH is adjusted in step (1) using hydrochloric acid.
4. The method of claim 1, wherein the calcification agent of step (2) is calcium oxide.
5. The method of claim 1, wherein the calcification agent is added in step (2) at a molar ratio of Ca/V (1-3) to 1.
6. The method of claim 1, wherein the calcification reaction of step (2) is at a temperature of 50-100 ℃.
7. The method of claim 1, wherein the calcification reaction time of step (2) is 0.2-2 h.
8. The method of claim 1, wherein the calcium vanadate obtained in step (2) is subjected to ammonification, dissolution, impurity removal, crystallization and calcination to obtain vanadium pentoxide.
9. The process of claim 1, wherein the sulfuric acid used in step (4) has a concentration of 10 to 98 wt.%.
10. The method of claim 1, wherein the ratio of the sulfuric acid to the chromium containing material in step (4) is (2-8): 1.
11. The method of claim 1, wherein the acid dissolution reaction in step (4) is carried out at a temperature of 30-90 ℃ for a reaction time of 0.5-2 h.
12. The method of claim 1, wherein the oxidant in step (4) is any one of air, ozone or hydrogen peroxide or a combination of at least two of air, ozone and hydrogen peroxide.
13. The method of claim 1, wherein the pH is adjusted by adding an acid-base modifier to the mixture of step (4), wherein the acid-base modifier is sulfuric acid, NaOH or Na2CO3Any one of them.
14. The method of claim 1, wherein the salt basicity is adjusted to 33% in step (4).
15. The method of claim 1, wherein the method comprises the steps of:
(1) regulating the pH value of the vanadium-chromium solution to 1.6-1.9 by using hydrochloric acid to carry out hydrolysis vanadium precipitation, and then carrying out solid-liquid separation to obtain a solid-phase red cake and a vanadium-chromium-containing vanadium-precipitation solution;
(2) mixing the red cake obtained in the step (1) with calcium oxide according to the molar ratio of Ca/V (1-3) to 1, adding the mixture into water, controlling the temperature to be 50-100 ℃ to carry out calcification reaction, carrying out solid-liquid separation after the reaction is carried out for 0.2-2h to obtain solid-phase calcium vanadate; carrying out ammonification, dissolving, impurity removal, crystallization and calcination on the obtained calcium vanadate to obtain vanadium pentoxide;
(3) adding polyferric chloride into the vanadium-precipitated liquid obtained in the step (1) to carry out secondary vanadium precipitation, then carrying out reduction chromium precipitation, and carrying out solid-liquid separation after the reaction is finished to obtain a chromium-containing material and a sodium salt solution; the obtained sodium salt solution can be returned to the sodium salt roasting process;
(4) adding the chromium-containing material obtained in the step (3) into sulfuric acid with the concentration of 10-98 wt% according to the liquid-solid ratio of (2-8):1, controlling the temperature to be 30-90 ℃ to carry out acid dissolution reaction for 0.5-2h, adding an oxidant after the reaction is finished, then adding an acid-base regulator to regulate the pH to be 2-4.6, carrying out solid-liquid separation to obtain a chromium sulfate solution, then adding NaOH to regulate the basicity to be 32-36%, and then evaporating and drying to obtain basic chromium sulfate; the oxidant air, ozone or hydrogen peroxide is any one or the combination of at least two of the oxidant air, ozone and hydrogen peroxide, and the acid and the alkali are adjustedThe agent is sulfuric acid, NaOH or Na2CO3Any one of them.
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| CN109399714B (en) * | 2018-12-29 | 2021-06-22 | 长沙兴嘉生物工程股份有限公司 | Method for preparing basic chromium sulfate from chromium-containing wastewater |
| CN110343866B (en) * | 2019-08-15 | 2021-09-28 | 攀钢集团钒钛资源股份有限公司 | Method for separating vanadium and chromium from vanadium and chromium reduction slag |
| CN111041205A (en) * | 2019-12-18 | 2020-04-21 | 昆明理工大学 | Method for separating vanadium and chromium from vanadium and chromium solution |
| CN113816847B (en) * | 2021-10-08 | 2023-09-19 | 上海良仁化工有限公司 | Method for preparing basic chromium acetate from chromium-containing sludge |
| CN113957262B (en) * | 2021-10-29 | 2022-09-23 | 东北大学 | Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium |
| CN114058846A (en) * | 2021-11-12 | 2022-02-18 | 四川省绵阳市华意达化工有限公司 | Method for circularly separating vanadium and chromium in vanadium-chromium solution by calcium salt |
| CN114703363B (en) * | 2022-03-17 | 2023-10-20 | 四川省银河化学股份有限公司 | Method for separating vanadium from chromium in high-chromium system |
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