CN111979431A - Production method of ammonium vanadate - Google Patents
Production method of ammonium vanadate Download PDFInfo
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- CN111979431A CN111979431A CN201910961695.2A CN201910961695A CN111979431A CN 111979431 A CN111979431 A CN 111979431A CN 201910961695 A CN201910961695 A CN 201910961695A CN 111979431 A CN111979431 A CN 111979431A
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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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of 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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a production process technology of ammonium vanadate (ammonium vanadate refers to ammonium metavanadate, ammonium polyvanadate and the like in the patent), which is an ammonium vanadate production process for extracting vanadium from vanadium-containing minerals, recovering vanadium from vanadium-containing catalysts and recovering vanadium from various solid wastes of metallurgical hazardous wastes. Belongs to the technical field of smelting extraction, high-valued treatment of hazardous waste recovery and high-valued treatment of solid waste recovery. The method is characterized in that no wastewater is generated in the ammonium vanadate production process, the process technical route of generating a large amount of wastewater in the traditional production process is completely changed, the production cost and the potential pollution to the environment caused by production are greatly reduced, and the method is a brand new ammonium vanadate production process with simplified production process, high recovery rate, large capacity, energy conservation, environmental protection, zero emission and environmental friendliness. The patent can also be used for extracting low-content vanadium ore, in the production process of the traditional vanadium extraction process, the vanadium pentoxide content in the vanadium-extracted waste slag material is 1-3%, so that the vanadium-extracted waste slag material can not be further extracted, the patent can be used for extracting low-content vanadium ore and recycling vanadium ore tailings and the waste slag material after smelting, and the recovery rate can reach 95%.
Description
Technical Field
The technical field of a method for producing ammonium vanadate (comprising ammonium metavanadate, ammonium polyvanadate and the like)
The technical field of a method for producing ammonium vanadate (comprising ammonium metavanadate, ammonium polyvanadate and the like) comprises the following steps: belongs to the technical field of smelting extraction, high-valued treatment of hazardous waste recovery and high-valued treatment of solid waste recovery.
Technical Field
Ammonium vanadate (including ammonium metavanadate, ammonium polyvanadate and the like) is a main raw material for producing vanadium pentoxide and other vanadium products.
At present, the production process of ammonium vanadate (including ammonium metavanadate, ammonium polyvanadate and the like) all over the world is divided into an acid leaching production process and an alkaline leaching production process, and the existing production process of ammonium vanadate has high production cost, and the leachate is used only once, so that after entering the production process of ammonium vanadate, wastewater is formed and discharged, and cannot be reused, and a large amount of wastewater is generated in the production process of ammonium vanadate. In addition, in the production process of the traditional vanadium extraction process, the vanadium pentoxide content of the slag after vanadium extraction is 1-3% and the slag is treated as a waste slag, so that vanadium in the slag can not be further extracted, and huge waste of resources is caused.
The process technology is innovative to ensure that the leaching solution can be reused, vanadium-containing salt crystals crystallized from the leaching solution are redissolved and purified by adjusting the pH value to be used for producing ammonium vanadate, and the leaching process and the ammonium vanadate production process are independently developed by the innovative process, so that the aim of reusing the leaching solution is fulfilled. The vanadium precipitation solution in the ammonium vanadate production process can also be used as a purification solution for dissolving vanadium-containing salt crystals and for producing ammonium vanadate. Thereby greatly reducing the generation of sewage in the production process and reducing the production cost. The production process is a brand new production process for ammonium vanadate, which has the advantages of simplification, high recovery rate, high productivity, energy conservation, environmental protection and environmental friendliness.
The process technology can also be used for extracting low-content vanadium ore, the vanadium pentoxide content in the slag material after vanadium extraction is 1-3% in the production process of the traditional vanadium extraction process at present, the process technology can be used for extracting low-content vanadium ore and recycling vanadium ore tailings and waste slag after smelting, and the recovery rate can reach 95%.
Vanadium is a silver-grey metal. The melting point is 1890 + -10 deg.C, which belongs to the high melting point rare metals. Its boiling point is 3380 deg.C, pure vanadium is hard, non-magnetic and ductile, but if it contains a small amount of impurities, especially nitrogen, oxygen, hydrogen, etc., it can obviously reduce its plasticity.
The vanadium is mainly used in the steel industry, and the vanadium is added into the steel, so that the elasticity and the strength of the steel are greatly improved, the steel has excellent wear resistance and explosion resistance, is high temperature resistant and cold resistant, and is used in the departments of automobiles, aviation, railways, electronic technology, national defense industry and the like. In addition, vanadium oxides have become one of the best catalysts in the chemical industry.
Vanadium is mainly used for manufacturing high-speed cutting steel and other alloy steels and catalysts. Vanadium steel can be made by mixing vanadium into steel. The vanadium steel is more compact than a common steel structure, and has higher toughness, elasticity and mechanical strength. The armor-piercing bullet made of vanadium steel can penetrate through a steel plate with the thickness of 40 cm.
Vanadium has many excellent physical and chemical properties, so that it has a wide range of applications, known as metal "vitamin". Most of the original vanadium is applied to steel, and the steel structure and crystal grains are refined, so that the crystal grain coarsening temperature is increased, and the strength, the toughness and the wear resistance of the steel are improved. Later, the excellent improvement effect of vanadium in titanium alloy is gradually discovered and applied to the field of aerospace, so that the aerospace industry is developed in a breakthrough manner. With the rapid development of the scientific and technical level, the requirements of human beings on new materials are increasingly improved. Vanadium is applied more and more widely in non-steel fields, and the application range of vanadium covers a plurality of fields such as aerospace, chemistry, batteries, pigments, glass, optics, medicines and the like.
Vanadium, monosodium glutamate in modern industry, is an indispensable important material for developing modern industry, modern national defense and modern scientific technology. Vanadium is used in the largest amount in the metallurgical industry. The consumption of vanadium in the steel industry accounts for 85% of its total production worldwide. Meanwhile, the application of vanadium in other fields such as chemical industry, vanadium batteries, aerospace and the like is continuously expanded, and the vanadium battery has a good development prospect.
Vanadium is mainly used as an alloying additive in the steel industry, and the development changes of the steel industry are crucial to predicting the demand of vanadium. That is, the trend of the demand of steel for vanadium determines the fate of the vanadium industry.
The yield of Chinese steel is about 6 hundred million tons, the average consumption intensity of vanadium per ton is increased by 10g, and the consumption intensity is reduced to about 1.1 ten thousand tons in terms of vanadium pentoxide. In the united states, carbon steel and high strength low alloy steel are the steel grades with the largest vanadium usage in the steel industry, accounting for more than 60% of vanadium usage in the steel industry, and high alloy steel is the second.
The vanadium battery is one of the outstanding green environment-friendly storage batteries (harmful substances are not generated in the manufacturing, using and discarding processes) which are strongly developed at present, has a special battery structure, and can discharge deeply with high current density; the charging is rapid; the specific energy is high; the price is low; the application field is very wide: for example, the power supply can be used as a standby power supply for buildings, airports and program-controlled exchange stations; can be used as a matched energy storage device of a solar energy and other clean power generation systems; the power supply device is used for supplying power to submarines and ocean-going ships, and is used for power grid peak regulation and the like.
The cost of the vanadium battery is similar to that of a lead-acid battery, and the vanadium battery can also be used for preparing a megawatt battery pack which can provide electric energy for a long time with high power, so that the vanadium battery has the cost performance advantage which is incomparable with that of a lithium ion battery and a nickel-hydrogen battery in the field of large-scale energy storage. The vanadium battery has simple production process, economic price and excellent electrical property, and has competitive strength in the aspect of application prospect of large-scale energy storage and power supply of electric vehicles compared with the fuel battery with complex manufacture and high price.
The 85 th international vanadium technology committee member will be held in the kyoto (9/25 th 2013), and the congress analyzes that in the next five years, the market consumption structure of global vanadium products cannot be changed greatly, and the vanadium products still belong to three application fields of steel (90-93%), non-ferrous alloy (4-5%) and chemical and functional materials (3-4%), but the product varieties are more serialized, diversified and functionalized on the basis of extension, the manufacturing, consumption and research and development center of the vanadium products is shifted to China, the China high-end vanadium products can basically realize localization, the consumption ratio of the vanadium-nitrogen alloy and the vanadium functional materials is further increased, and the market consumption total amount of the Chinese vanadium products is increased to 8-9 ten thousand tons/2015 from the current 5-6 ten thousand tons/2015; the total market consumption of global vanadium products will be increased from 12-13 ten thousand tons/year to 16-18 ten thousand tons/year (2015); the vanadium battery energy storage technology is expected to begin to form industrial application in about 2018, and at the moment, the market of vanadium products is increased to a large consumption field, so that the prospect of the world vanadium industry is bright.
The invention content is as follows:
adding catalyst, oxidant, surfactant and defoaming agent into water. After stirring and dissolving, adding the vanadium-containing material into the solution, wherein the solid-to-liquid ratio is 1: 0.5-1: 5, stirring for 10-50 minutes, heating to 80-95 ℃, and keeping the temperature for 10-50 minutes. Then adding prepared sodium hydroxide or sodium carbonate and hydrogen peroxide (or not) leaching solution, wherein the content of the sodium hydroxide is 10-300g/L, the content of the hydrogen peroxide is 0.1-20g/L, and the solid-liquid ratio is 1: 2-1: 6. Heating to 80-95 ℃, keeping the temperature for 30-120 minutes, then obtaining a vanadium-containing solution through hot-press filtration and slag washing processes, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 10-30 ℃ to obtain crystallized vanadium-containing salt crystals, separating the vanadium-containing salt crystals from a filtrate through pressure filtration, and supplementing a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) into the filtrate (or not) for returning the filtrate to be used as a leaching solution for repeated use, thereby completely changing the current situation that the leaching solution is used only once in the traditional production of ammonium vanadate salt at present and greatly reducing the generation of waste water.
Preparing the crystal obtained after filter pressing into an aqueous solution with a solid-liquid ratio of 1: 1-1: 20, stirring and dissolving, adjusting the pH value to 6-8, filter pressing and removing impurities, adding ammonium chloride, ammonium sulfate or other ammonium inorganic salts into the filter pressing solution, precipitating vanadium to generate ammonium vanadate precipitate, separating the ammonium vanadate salt from the vanadium precipitation solution through filter pressing, and returning the vanadium precipitation solution for repeated use to produce the ammonium vanadate precipitate. The method completely changes the current situation that the vanadium precipitation solution can only be used once in the traditional ammonium vanadate salt production, greatly reduces the generation of waste water and realizes zero discharge of sewage.
Drawings
The attached drawing is a process flow chart of the process.
The specific implementation mode is as follows:
1. mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 2, and stirring for 42 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirred for 42 minutes to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
Adding sodium hydroxide or sodium carbonate and oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, and potassium salt) into the water for preparing the leaching solution, stirring for 47 minutes, and dissolving. The content of sodium hydroxide or sodium carbonate is 110g/L, and the content of oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) is 11 g/L.
Stirring and heating the prepared vanadium-containing material pulping liquid to 81 ℃, and keeping the temperature for 37 minutes.
Preparing the heated vanadium-containing material into slurry and leaching solution, and mixing and stirring according to the proportion of 1: 4. Heating to 81 ℃, keeping the temperature for 80 minutes, then obtaining vanadium-containing solution through hot press filtration and slag washing processes, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 27 ℃ to obtain crystallized vanadium-containing salt crystals, separating the vanadium-containing salt crystals from vanadium-containing salt crystal pressure filtrate through press filtration, and returning the vanadium-containing salt crystal pressure filtrate to be used as leachate. The vanadium salt-containing crystal pressure filtrate is supplemented with a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) (or not added), and is returned to be used as a leaching solution for repeated use.
And (3) vanadium precipitation step: preparing vanadium-containing salt crystals into an aqueous solution with a solid-to-liquid ratio of 1: 6, stirring and dissolving, adjusting the pH value to be 8, hydrolyzing impurities to generate hydroxide to form a precipitate, carrying out filter pressing and impurity removal, adding ammonium inorganic salts such as ammonium chloride or ammonium sulfate into a filter pressing solution, adding the ammonium inorganic salts in a ratio of 1: 2-1: 5, stirring and reacting to precipitate vanadium to generate an ammonium vanadate precipitate, separating the ammonium vanadate salt from the vanadium precipitation solution through filter pressing, and returning the vanadium precipitation solution to be used as the vanadium precipitation solution to replace the aqueous solution for dissolving the vanadium-containing salt crystals in the vanadium precipitation step for repeated use to produce the ammonium vanadate precipitate. The method completely changes the current situation that the vanadium precipitation solution can be used only once in the traditional ammonium vanadate salt production, and greatly reduces the generation of waste water.
2. Mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 2.7, and stirring for 27 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirred for 36 minutes to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
Adding sodium hydroxide or sodium carbonate and oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, and potassium salt) into the water for preparing the leaching solution, and stirring for 46 min to dissolve. The content of sodium hydroxide or sodium carbonate is 10-300g/L, and the content of oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, potassium salt) is 12 g/L.
Stirring and heating the prepared vanadium-containing material pulping liquid to 86 ℃, and keeping the temperature for 36 minutes.
Adding small amount of sodium hydroxide or sodium carbonate and oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, and potassium salt) or not, and mixing at a ratio of 1: 4. Heating to 87 ℃, keeping the temperature for 90 minutes, then obtaining vanadium-containing solution through hot-press filtration and slag washing processes, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 22 ℃ to obtain crystallized vanadium-containing salt crystals, separating the vanadium-containing salt crystals from vanadium-containing salt crystal pressure filtrate through pressure filtration, and returning the vanadium-containing salt crystal pressure filtrate to be used as leachate. The vanadium salt-containing crystal pressure filtrate is supplemented with a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) (or not added), and is returned to be used as a leaching solution for repeated use.
And (3) vanadium precipitation step: preparing vanadium precipitation solution with a solid-liquid ratio of vanadium-containing salt crystal and vanadium solution of 1: 9, stirring and dissolving, adjusting the pH value to 7.5, hydrolyzing impurities to generate hydroxide to form precipitate, removing impurities through pressure filtration, adding ammonium inorganic salts such as ammonium chloride or ammonium sulfate into the pressure filtrate in a ratio of 1: 2, stirring and reacting to precipitate vanadium to generate ammonium vanadate precipitate, separating the ammonium vanadate salt from the vanadium precipitation solution through pressure filtration, and returning the vanadium precipitation solution to be used as the vanadium precipitation solution to replace the vanadium-containing salt crystal aqueous solution dissolved in the vanadium precipitation step for repeated use to produce the ammonium vanadate precipitate.
3. Mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 2.5, and stirring for 33 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirred for 33 minutes to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
Stirring and heating the prepared vanadium-containing material pulping liquid to 86 ℃, and keeping the temperature for 46 minutes.
Adding a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) or not added into the heated and constant-temperature vanadium-containing material pulping liquid and vanadium-containing salt crystal pressure filtrate, returning the mixture as a leaching solution, and mixing and stirring the mixture according to the proportion of 1: 3. Heating to 85 ℃, keeping the temperature for 45 minutes, then carrying out hot-press filtration and slag washing processes to obtain a vanadium-containing solution, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 25 ℃ to obtain crystallized vanadium-containing salt crystals, carrying out pressure filtration to separate the vanadium-containing salt crystals from the vanadium-containing salt crystal pressure filtrate, and returning the vanadium-containing salt crystal pressure filtrate to be used as a leaching solution.
And (3) vanadium precipitation step: preparing vanadium precipitation solution with the vanadium salt crystal and the vanadium solution in a solid-to-liquid ratio of 1: 6, stirring and dissolving, adjusting the pH value to be 7, hydrolyzing impurities to generate hydroxide to form precipitate, performing filter pressing to remove impurities, adding ammonium inorganic salt such as ammonium chloride or ammonium sulfate into filter pressing solution, adding ammonium inorganic salt with the proportion of 1: 2, stirring and reacting to precipitate vanadium to generate ammonium vanadate precipitate, and performing filter pressing to separate the ammonium vanadate salt from the vanadium precipitation solution. The vanadium precipitation solution is returned to be used as a solution for dissolving vanadium-containing salt crystals.
4. Mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 2.5, and stirring for 33 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirred for 33 minutes to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
Stirring and heating the prepared vanadium-containing material pulping liquid to 86 ℃, and keeping the temperature for 46 minutes.
Adding a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) or not added into the heated and constant-temperature vanadium-containing material pulping liquid and vanadium-containing salt crystal pressure filtrate, returning the mixture as a leaching solution, and mixing and stirring the mixture according to the proportion of 1: 3. Heating to 85 ℃, keeping the temperature for 45 minutes, then carrying out hot-press filtration and slag washing processes to obtain a vanadium-containing solution, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 25 ℃ to obtain crystallized vanadium-containing salt crystals, carrying out pressure filtration to separate the vanadium-containing salt crystals from the vanadium-containing salt crystal pressure filtrate, and returning the vanadium-containing salt crystal pressure filtrate to be used as a leaching solution.
And (3) vanadium precipitation step: preparing vanadium precipitation solution with the vanadium salt crystal and the vanadium solution in a solid-to-liquid ratio of 1: 6, stirring and dissolving, adjusting the pH value to be 7, hydrolyzing impurities to generate hydroxide to form precipitate, performing filter pressing to remove impurities, adding ammonium inorganic salt such as ammonium chloride or ammonium sulfate into filter pressing solution, adding ammonium inorganic salt with the proportion of 1: 2, stirring and reacting to precipitate vanadium to generate ammonium vanadate precipitate, and performing filter pressing to separate the ammonium vanadate salt from the vanadium precipitation solution. The vanadium precipitation solution is returned to be used as a solution for dissolving vanadium-containing salt crystals.
5. Mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 2.5, and stirring for 33 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirred for 33 minutes to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
Stirring and heating the prepared vanadium-containing material pulping liquid to 86 ℃, and keeping the temperature for 46 minutes.
Adding a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) or not added into the heated and constant-temperature vanadium-containing material pulping liquid and vanadium-containing salt crystal pressure filtrate, returning the mixture as a leaching solution, and mixing and stirring the mixture according to the proportion of 1: 3. Heating to 85 ℃, keeping the temperature for 45 minutes, then carrying out hot-press filtration and slag washing processes to obtain a vanadium-containing solution, adding a vanadium-containing salt agent crystallizing agent (or not), cooling to 25 ℃ to obtain crystallized vanadium-containing salt crystals, carrying out pressure filtration to separate the vanadium-containing salt crystals from the vanadium-containing salt crystal pressure filtrate, and returning the vanadium-containing salt crystal pressure filtrate to be used as a leaching solution.
And (3) vanadium precipitation step: dissolving vanadium precipitation solution prepared from vanadium salt-containing crystal precipitate and vanadium solution in a solid-to-liquid ratio of 1: 6, adjusting pH to 7, hydrolyzing impurities to generate hydroxide to form precipitate, removing impurities by pressure filtration, adding ammonium inorganic salt such as ammonium chloride or ammonium sulfate into the filtrate, adding ammonium inorganic salt in a ratio of 1: 2, stirring to react and precipitate vanadium to generate ammonium vanadate precipitate, and separating the ammonium vanadate salt from the vanadium precipitation solution by pressure filtration. The vanadium precipitation solution is returned to be used as a solution for dissolving vanadium-containing salt crystals.
In the specific implementation, the recovery rate of vanadium is more than 95 percent, and the purity of vanadium pentoxide after ammonium vanadate pyrolysis is more than 98 percent.
Claims (7)
1. A process for preparing ammonium vanadate (ammonium metavanadate, ammonium polyvanadate, etc.) includes preparing the slurry of vanadium-contained material, preparing the leaching liquid, repeating the use of leaching liquid, preparing vanadium-contained salt, cooling, crystallizing, dissolving crystal of vanadium-contained salt, regulating pH value, press filtering, adding ammonium salt (ammonium chloride, ammonium sulfate, etc.) to prepare ammonium vanadate salt, press filtering to obtain ammonium vanadate product, and returning the separated vanadium-contained liquid back to the solution for dissolving crystal of vanadium-contained salt. The method is characterized in that: (1) preparing slurry of vanadium-containing material, mixing vanadium-containing material and slurry for pulping, (2) preparing leachate (adding a supplement reagent into leaching pressure filtrate at the later stage), mixing the leachate and the vanadium-containing material slurry, stirring, heating for leaching, and pressure filtering, (3) repeatedly using the leachate, (4) preparing vanadium-containing salt, cooling for crystallization, adding a vanadium salt generating reagent into the leachate to generate vanadium salt crystals, (5) adding water into the vanadium salt crystals (adding vanadium precipitation pressure filtrate at the later stage) for dissolving, regulating the pH value, and performing pressure filtering and purification, (6) adding ammonium salt (ammonium chloride or ammonium sulfate and the like) into the vanadium salt crystal solution purified pressure filtrate to prepare ammonium vanadate salt, after generating ammonium vanadate salt precipitate, separating the ammonium vanadate salt and the vanadium precipitation pressure filtrate through pressure filtering, and (7) dissolving the vanadium precipitation pressure filtrate into the vanadium-containing crystal solution for repeatedly using.
2. The preparation method for pulping the vanadium-containing material according to claim 1 comprises the following steps: mixing and stirring the vanadium-containing material and the pulping liquid for pulping, wherein the solid-liquid ratio is 1: 0.5-1: 5, and stirring for 10-50 minutes. The preparation method of the pulping liquid comprises the following steps: adding catalyst, oxidant, surfactant and defoaming agent into water. Stirring for 10-50 min to dissolve. The catalyst is oxide, sulfide, etc., the oxidant is sodium salt, potassium salt, manganese salt, ammonium salt, etc., the surfactant is sulfonate, sodium salt, etc., and the defoaming agent is nitrate, phosphate, etc.
3. Adding sodium hydroxide or sodium carbonate and oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, and potassium salt) into the water for preparing the leaching solution, stirring for 10-50 min, and dissolving. The content of sodium hydroxide or sodium carbonate is 10-300g/L, and the content of oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt, potassium salt) is 0.1-20 g/L.
4. Stirring and heating the prepared vanadium-containing material pulping liquid to 80-95 ℃, and keeping the temperature for 10-50 minutes.
5. The heated vanadium-containing material is made into slurry and leaching solution, and the slurry and the leaching solution are mixed and stirred according to the proportion of 1: 2-1: 6. Heating to 80-95 ℃, keeping the temperature for 30-120 minutes, then carrying out hot-press filtration and slag washing processes to obtain a vanadium-containing solution, adding a vanadium-containing salt agent crystallization agent (or not), cooling to 10-30 ℃ to obtain crystallized vanadium-containing salt crystals, carrying out pressure filtration to separate the vanadium-containing salt crystals from the vanadium-containing salt crystal pressure filtrate, and returning the vanadium-containing salt crystal pressure filtrate to be used as a leaching solution. The vanadium salt-containing crystal pressure filtrate is supplemented with a small amount of sodium hydroxide or sodium carbonate and an oxidant (such as hydrogen peroxide, manganese dioxide, sodium salt and potassium salt) (or not added), and is returned to be used as a leaching solution for repeated use.
6. And (3) vanadium precipitation step: preparing the vanadium-containing crystal into an aqueous solution with a solid-to-liquid ratio of 1: 1-1: 20, stirring and dissolving, adjusting the pH value to 6-8, hydrolyzing impurities to generate hydroxide to form a precipitate, removing impurities by pressure filtration, adding ammonium inorganic salts such as ammonium chloride or ammonium sulfate into the pressure filtrate in a ratio of 1: 2-1: 5, stirring and reacting to precipitate vanadium to generate an ammonium vanadate precipitate, separating the ammonium vanadate salt from the vanadium precipitation solution by pressure filtration, and returning the vanadium precipitation solution to be used as the vanadium precipitation solution to replace the aqueous solution of the vanadium-containing crystal dissolved in the vanadium precipitation step for repeated use to produce the ammonium vanadate precipitate. The method completely changes the current situation that the vanadium precipitation solution can be used only once in the traditional ammonium vanadate salt production, and greatly reduces the generation of waste water. And (4) zero discharge of sewage.
7. The process technology can be used for extracting low-content vanadium ore, the vanadium pentoxide content in the slag material after vanadium extraction is 1-3% in the production process of the traditional vanadium extraction process, the process technology can not be further extracted, the process technology can be used for extracting low-content vanadium ore, recycling vanadium ore tailings and waste slag material after smelting, high-value treatment is carried out, and the recovery rate can reach 95%.
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| CN105400967A (en) * | 2015-11-10 | 2016-03-16 | 中国科学院过程工程研究所 | Method for extracting chromium and vanadium from vanadium slag at low temperature and normal pressure |
| CN107760868A (en) * | 2017-11-06 | 2018-03-06 | 中南大学 | A kind of method that vanadium, chromium and sodium carbonate salt are separated and recovered in the liquid from Leaching of Vanadium from Vanadium slag |
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| CN101899582A (en) * | 2010-07-30 | 2010-12-01 | 四川省川威集团有限公司 | Method for extracting vanadium pentoxide from vanadium slag |
| CN104477992A (en) * | 2015-01-07 | 2015-04-01 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide |
| CN105400967A (en) * | 2015-11-10 | 2016-03-16 | 中国科学院过程工程研究所 | Method for extracting chromium and vanadium from vanadium slag at low temperature and normal pressure |
| CN107760868A (en) * | 2017-11-06 | 2018-03-06 | 中南大学 | A kind of method that vanadium, chromium and sodium carbonate salt are separated and recovered in the liquid from Leaching of Vanadium from Vanadium slag |
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| CN113684376A (en) * | 2021-07-19 | 2021-11-23 | 宁波双能环保科技有限公司 | Method for extracting vanadium from magnesium sulfate phosphorus slag by using high-pressure kettle |
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