CN112408478A - Preparation method of vanadium trioxide - Google Patents
Preparation method of vanadium trioxide Download PDFInfo
- Publication number
- CN112408478A CN112408478A CN202011404547.XA CN202011404547A CN112408478A CN 112408478 A CN112408478 A CN 112408478A CN 202011404547 A CN202011404547 A CN 202011404547A CN 112408478 A CN112408478 A CN 112408478A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- solid
- product
- gas
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention provides a preparation method of vanadium trioxide, which comprises the following steps: mixing vanadate, an auxiliary agent and a reducing agent to perform a reduction reaction to obtain reduction clinker; and mixing the obtained reduction clinker with water, and carrying out solid-liquid separation to obtain a first solid product and a first separation solution, wherein the first solid product is dried to obtain a vanadium trioxide product. The method adopts a solid phase transformation regulation and control technology, realizes the separation of vanadium and alkali metal by adding an auxiliary agent, and directly reduces and prepares a vanadium trioxide product; the method disclosed by the invention does not need high-temperature liquid phase dissociation, avoids the inoperability of a high-temperature high-pressure reaction system, is simple in process flow, mild and safe in operation conditions, low in operation cost, high in vanadium yield, beneficial to industrial large-scale production and good in industrial application prospect.
Description
Technical Field
The invention belongs to the field of nonferrous metallurgy, and particularly relates to a preparation method of vanadium trioxide.
Background
Vanadium is used as an important metal resource in China, is called industrial monosodium glutamate, has main products of vanadium pentoxide, vanadium trioxide, vanadium-nitrogen alloy, ferrovanadium alloy, vanadium-aluminum alloy and the like, and can be widely used in the fields of steel, chemical industry, national defense, electronics, manufacturing, energy storage, medicine, catalysis and the like.
Among them, vanadium trioxide, which is one of the important vanadium products, can be used for preparing various gas sensors, memory materials, resistive materials, etc. due to its excellent optical, electrical, and magnetic properties. The production method of vanadium trioxide is mainly divided into 4 types: one is vanadium slag roasting-leaching-ammonium salt vanadium precipitation-calcining to obtain vanadium pentoxide, and the vanadium pentoxide is reduced to obtain vanadium trioxide or the ammonium salt of the vanadium is directly reduced, roasted or thermally cracked to obtain the vanadium trioxide, and the technical route is relatively mature and widely applied, but the problems are also obvious: from vanadium extraction to product preparation, operations such as acid addition, ammonium addition, high-salt high-ammonia nitrogen wastewater treatment and the like are required, the process is long, the energy consumption is large, the automation degree is low, and the operation cost is high; in the preparation process of ammonium vanadate, pH is required to be adjusted by acid and a large amount of ammonium salt is required to precipitate vanadium, so that a large amount of wastewater containing ammonia nitrogen and sodium salt is generated, and the environmental safety is threatened; the calcination of ammonium vanadate to produce vanadium oxide results in inorganized ammonia emission, worsening of working environment and environmental pollution.
And the second method is a method for preparing vanadium trioxide by electrodialysis of a sodium vanadate solution, wherein vanadium and sodium ions are selectively separated by an ionic membrane so as to obtain sodium hydroxide and vanadic acid, and the vanadic acid is further reduced and roasted to obtain the vanadium trioxide. CN 103101976A discloses a method for preparing vanadium trioxide powder by vanadate reduction, which comprises the following steps: and (2) introducing direct current into an alkaline solution containing vanadate to perform an electrolytic reaction to obtain a vanadium-containing precursor, separating, washing and drying the precursor, and then reducing in a reducing atmosphere to obtain crude vanadium trioxide. The method belongs to a conventional method for separating anions and cations by electrodialysis, and the total current efficiency is about 60 percent, the current efficiency is low because hydrogen leakage and hydroxyl leakage of an ionic membrane cannot be avoided, the ionic membrane has high requirement on the cleanliness of a solution, the raw material adaptability of the technology is poor, no industrialization condition is provided at present, and further technology upgrading is still needed.
The third method is that sodium vanadate solution is subjected to high-pressure high-temperature hydrothermal reduction to prepare vanadium trioxideThe method comprises the steps of introducing hydrogen into a solution at high temperature and high pressure to reduce pentavalent vanadium into trivalent vanadium, hydrolyzing the trivalent vanadium to obtain a hydrolysate of vanadium trioxide, and calcining the hydrolysate to obtain the vanadium trioxide. CN107434259A discloses a method for preparing vanadium trioxide from a vanadium-containing solution, which comprises the following steps: introducing CO into the vanadium-containing solution2And H2Reacting under the conditions of heating and pressurizing, and performing solid-liquid separation after the reaction is finished to obtain vanadium trioxide solid and a second separation solution. The method has the advantages of high reaction temperature, 1-2.5 Mpa of hydrogen partial pressure, high risk and large industrialization difficulty, and the comprehensive partial pressure of a reaction system is up to dozens of Mpa, and the process is extremely sensitive to acidity and needs to be neutralized by sulfuric acid, so the problem of high-salinity wastewater is not solved, and the method has no application condition for preparing bulk vanadium products.
The fourth is a direct reduction with the addition of a reducing agent, e.g. C, CO, CH4，H2And para V such as vanadium metal5+And (4) carrying out reduction. CN106629847A discloses a method for preparing vanadium trioxide by vanadate, which comprises the following steps: using vanadate as a raw material, reducing by carbon-containing reducing gas at the temperature of 125-629 ℃ to obtain a reduction product consisting of vanadium trioxide and sodium carbonate, adding water into the reduction product to dissolve the sodium carbonate in the reduction product, filtering, washing and drying a filter cake to obtain a vanadium trioxide product, and using CO to dissolve a dissolving solution2Acidifying, crystallizing, separating and recovering sodium carbonate salt; the process relies on the acidic oxidation product CO2The solid phase sodium removal property of the method bypasses the generation region of sodium vanadate to prepare vanadium trioxide products, but based on the recognition of the characteristics of vanadium oxide and sodium carbonate, the technology can not completely realize the conversion of sodium vanadate to vanadium trioxide and sodium carbonate, and the yield is low.
In conclusion, the existing method for preparing vanadium trioxide mostly uses ammonium vanadate as a raw material, and has the disadvantages of long flow, high energy consumption and serious three-waste pollution; although part of new technologies appear, the defects of the technologies are too obvious, and the industrialization possibility is not available at present, so that a preparation method of vanadium trioxide, which is simple in process, green and clean and low in production and operation cost, is urgently needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of vanadium trioxide, wherein the preparation method adopts a solid phase transformation regulation and control technology, realizes the separation of vanadium and alkali metal by adding an auxiliary agent, and directly reduces and prepares the vanadium trioxide; the preparation method has the advantages of simple process flow, mild and safe operation conditions, low operation cost, high vanadium yield and good industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing vanadate, an auxiliary agent and a reducing agent to perform a reduction reaction to obtain reduced clinker;
(2) and (2) mixing the reduction clinker obtained in the step (1) with water, and carrying out solid-liquid separation to obtain a first solid product and a first separation solution, wherein the first solid product is dried to obtain a vanadium trioxide product.
According to the method, the binding capacity of an auxiliary agent and metal cations in vanadate is greater than that of vanadate ions and the metal cations, and the dissociation of the vanadate ions and the metal cations in the vanadate is realized at high temperature by adding the auxiliary agent, so that the generation of hypovanadate is avoided, and vanadium trioxide is prepared by direct reduction; the preparation method adopts a solid phase transformation regulation and control technology, does not need high-temperature liquid phase dissociation, avoids the difficult operability of a high-temperature high-pressure reaction system, has simple process flow, low cost and high vanadium yield, and is beneficial to industrial application.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the vanadate in step (1) comprises any one or a combination of at least two of orthovanadate, pyrovanadate and metavanadate, and typical but non-limiting examples of the combination are: combinations of orthovanadate and pyrovanadate, combinations of pyrovanadate and metavanadate, combinations of orthovanadate, pyrovanadate and metavanadate, and the like.
Preferably, the orthovanadate comprises sodium orthovanadate and/or potassium orthovanadate.
Preferably, the pyrovanadate comprises sodium pyrovanadate and/or potassium pyrovanadate.
Preferably, the metavanadate comprises sodium metavanadate and/or potassium metavanadate.
In the present invention, the selection of vanadate having the same cation is advantageous for subsequent application to the product.
Preferably, the adjuvant of step (1) comprises any one of an amphoteric compound, a weak acid or an acidic oxide, or a combination of at least two of these, typical but non-limiting examples being: combinations of amphoteric compounds and weak acids, combinations of weak acids and acidic oxides, amphoteric compounds and acidic oxides, and the like.
Preferably, the amphoteric compound comprises aluminum oxide and/or aluminum hydroxide.
Preferably, the weak acid comprises silicic acid and/or boric acid.
Preferably, the acidic oxide comprises silica and/or phosphorus pentoxide.
As a preferable technical scheme of the invention, the reducing agent in the step (1) comprises a solid reducing agent and/or a reducing gas.
Preferably, the solid reducing agent comprises carbon.
Preferably, the reducing gas comprises any one or a combination of at least two of carbon monoxide, hydrogen, coal gas or natural gas, typical but non-limiting examples of which are: a combination of carbon monoxide and hydrogen, a combination of hydrogen and gas, a combination of carbon monoxide, gas and natural gas, and the like.
In a preferred embodiment of the present invention, the mass ratio of the auxiliary agent to vanadate in step (1) is (0.2 to 3: 1), for example, 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1 or 3:1, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
In the invention, the addition ratio of the auxiliary agent needs to be controlled. If the addition amount of the auxiliary agent is too much, the auxiliary agent is remained in the vanadium trioxide, and the product quality is influenced; if the addition amount of the auxiliary agent is too small, the content of sodium and/or potassium in the vanadium trioxide exceeds the standard, and the grade is reduced.
In the invention, the addition amount of the reducing agent is determined according to the selected type and the addition of vanadate and an auxiliary agent, and is specifically 1.05-1.2 times of the theoretical value of completely reducing vanadium in vanadate. If the addition amount of the solid reducing agent is too much, the reducing agent is remained in the vanadium trioxide, and resources are wasted; if the addition amount of the reducing agent is too small, vanadium in vanadate can not be sufficiently oxidized, and the product quality is influenced.
In a preferred embodiment of the present invention, the reaction temperature of the reduction reaction in the step (1) is 650 to 900 ℃, for example 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable, and preferably 700 to 850 ℃.
In the present invention, the reduction temperature has a crucial influence on the recovery rate of vanadium. If the reduction temperature is too low, the reduction is not thorough, and a qualified vanadium trioxide product cannot be obtained; if the reduction temperature is too high, the material is melted, separation is difficult, and energy is wasted.
Preferably, the reduction reaction in step (1) is carried out for 3-5 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the material after the reduction reaction in the step (1) is cooled.
Preferably, the material after the reduction reaction in step (1) is cooled in a non-oxidizing atmosphere.
In the invention, the material after the reduction reaction in the step (1) is cooled to normal temperature under non-oxidizing atmosphere.
Preferably, the non-oxidizing atmosphere comprises a protective gas and/or a reducing gas.
Preferably, the protective gas comprises nitrogen and/or argon.
Preferably, the reducing gas comprises any one or a combination of at least two of carbon monoxide, hydrogen, coal gas or natural gas, typical but non-limiting examples of which are: a combination of carbon monoxide and hydrogen, a combination of hydrogen and gas, a combination of carbon monoxide, gas and natural gas, and the like.
In the invention, non-oxidizing gas is introduced during cooling to prevent the reduced trivalent vanadium from being oxidized again.
In a preferred embodiment of the present invention, the solid-to-liquid ratio of the reduced clinker to water in step (2) is 0.2 to 0.5g/ml, for example, 0.2g/ml, 0.25g/ml, 0.3g/ml, 0.35g/ml, 0.4g/ml, 0.45g/ml, or 0.5g/ml, but not limited to the above-mentioned values, and other values not listed in this range are also applicable, and preferably 0.25 to 0.33 g/ml.
Preferably, the mixing of step (2) is followed by washing.
Preferably, the washing temperature is 30 to 90 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 40 to 80 ℃.
Preferably, the washing time is 1 to 2 hours, such as 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying temperature in step (2) is 80 to 160 ℃, for example 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 100 to 140 ℃.
Preferably, the drying time in step (2) is 1-2 h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the first separated solution in the step (2) is carbonated.
In the present invention, CO is introduced into the obtained first separated solution2And carrying out carbonation treatment.
Preferably, the temperature of the carbonation treatment is 20 to 40 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 25 to 30 ℃.
Preferably, the pH of the carbonated solution is 7 to 9, such as 7, 7.5, 8, 8.5, or 9, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 7.5 to 8.5.
As a preferable technical solution of the present invention, after the carbonation treatment, solid-liquid separation is performed to obtain a second solid product and a second separated solution.
Preferably, the second solid product is returned to step (1) as an adjuvant.
In the invention, the obtained second solid product still can be doped with unseparated vanadium, and the second solid product is used as an auxiliary agent and returned to the step (1) for circulation, so that the resource utilization is maximized and the yield of the vanadium is improved.
Preferably, the second separation solution is used for vanadium slag leaching or evaporation concentration, cooling and crystallization to obtain carbonate and/or bicarbonate.
Preferably, the carbonate and/or bicarbonate is sold as a product or used in vanadium slag roasting.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing an auxiliary agent and vanadate with a mass ratio of (0.2-3): 1 with a reducing agent, carrying out a reduction reaction at 650-900 ℃ for 3-5 h, and cooling the reacted material in a non-oxidizing atmosphere to obtain a reduction clinker; the vanadate comprises any one or a combination of at least two of orthovanadate, pyrovanadate or metavanadate, the auxiliary comprises any one or a combination of at least two of amphoteric compounds, weak acids or acidic oxides, the reducing agent comprises any one or a combination of at least two of carbon, carbon monoxide, hydrogen, coal gas or natural gas, and the non-oxidizing gas comprises a protective gas and/or a reducing gas;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-liquid ratio of 0.2-0.5 g/ml, washing for 1-2 hours at 30-90 ℃, then carrying out solid-liquid separation to obtain a first solid product and a first separation solution, and drying the first solid product for 1-2 hours at 80-160 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 20-40 ℃, and carrying out solid-liquid separation after the pH value reaches 7-9 to obtain a second solid product and a second separation solution;
the second solid product is used as an auxiliary agent and returned to the step (1), and the second separation solution is used for leaching vanadium slag or is subjected to evaporation concentration, cooling and crystallization to obtain carbonate and/or bicarbonate; the carbonate and/or bicarbonate is sold as a product or used in vanadium slag roasting.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method adopts a solid phase transformation regulation and control technology, realizes the separation of vanadium and alkali metal by adding the auxiliary agent, and directly reduces and prepares the vanadium trioxide, compared with the prior art, the method does not need high-temperature liquid phase dissociation, avoids the difficult operability of a high-temperature high-pressure reaction system, and has the advantages of simple process flow, mild and safe operation conditions and low operation cost; the preparation method further controls the addition of the auxiliary agent and the temperature of the reduction reaction, so that the comprehensive yield of the vanadium reaches more than 97 percent; the purity of vanadium trioxide is more than 96 percent, the content of alkali metal in vanadium trioxide products is less than 0.4 percent, and the quality meets the preparation requirement of vanadium alloy products.
(2) According to the preparation method, vanadate is used as a raw material to prepare vanadium trioxide through direct reduction, and compared with the traditional method, the processes of acid regulation, ammonium addition, high ammonia nitrogen and high salinity wastewater treatment and the like in the ammonium vanadate preparation process are omitted; and the medium is circulated in a closed loop, no high ammonia nitrogen and high salt wastewater is generated, no solid wastewater is discharged, no ammonia gas is discharged, the process is green and clean, and the environment is friendly.
Drawings
FIG. 1 is a process flow diagram of a method for preparing vanadium trioxide according to the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention partially provides a preparation method of vanadium trioxide, as shown in fig. 1, the preparation method comprises the following steps:
(1) mixing an auxiliary agent, vanadate and a reducing agent to perform a reduction reaction to obtain a reduction clinker;
(2) mixing the reduction clinker obtained in the step (1) with water, washing, and carrying out solid-liquid separation to obtain a first solid product and a first separation solution, wherein the first solid product is dried to obtain a vanadium trioxide product;
separating the first separated solution from CO2Mixing, performing carbonation treatment, and performing solid-liquid separation to obtain a second solid product and a second separation solution;
and (3) returning the second solid product as an auxiliary agent to the step (1), wherein the second separation solution is used for leaching vanadium slag or is subjected to evaporation concentration, cooling crystallization and is used for recovering carbonate and/or bicarbonate.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 100g of sodium orthovanadate and 150g of aluminum hydroxide, introducing 700ml/min of coke oven gas, carrying out reduction reaction at 750 ℃, reacting for 3 hours, and cooling the reacted materials to 30 ℃ under the nitrogen atmosphere to obtain reduced clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.33g/ml, washing for 1h at 50 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 2h at 100 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 20 ℃, filtering and separating after the pH value reaches 7 to obtain a second solid product and a second separation solution;
and (3) returning the second solid product as an auxiliary agent to the step (1), wherein the second separation solution is used for leaching vanadium slag.
Example 2:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 100g of sodium orthovanadate and 300g of boric acid, introducing 500ml/min of hydrogen, carrying out reduction reaction at 800 ℃ for 4 hours, and cooling the reacted materials to 30 ℃ under the argon atmosphere to obtain reduced clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.25g/ml, washing for 2 hours at 50 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 1.5 hours at 110 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 30 ℃, filtering and separating after the pH value reaches 8 to obtain a second solid product and a second separation solution;
returning the second solid product serving as an auxiliary agent to the step (1), evaporating and concentrating the second separated solution, cooling and crystallizing to obtain sodium carbonate and sodium bicarbonate; the sodium carbonate and sodium bicarbonate are sold as products or used for roasting vanadium slag.
Example 3:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 100g of sodium pyrovanadate and 40g of silicon dioxide, introducing 600ml/min of carbon monoxide, carrying out reduction reaction at 700 ℃, reacting for 5 hours, and cooling the reacted materials to 30 ℃ under the atmosphere of nitrogen and hydrogen to obtain reduction clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.33g/ml, washing for 1.5h at 50 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 1h at 120 ℃ to obtain a vanadium trioxide product;
carbonating the first separation solution at 40 ℃, filtering and separating after the pH value reaches 8 to obtain a second solid product and a second separation solution;
and (3) returning the second solid product as an auxiliary agent to the step (1), wherein the second separation solution is used for leaching vanadium slag.
Example 4:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 80g of sodium metavanadate, 20g of potassium metavanadate and 20g of silicon dioxide, adding 2.5g of carbon, carrying out reduction reaction at 700 ℃, reacting for 3.5h, and cooling the reacted materials to 30 ℃ under the atmosphere of nitrogen to obtain reduction clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.33g/ml, washing for 2 hours at 50 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 1 hour at 120 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 25 ℃, filtering and separating after the pH value reaches 9 to obtain a second solid product and a second separation solution;
and (3) returning the second solid product as an auxiliary agent to the step (1), wherein the second separation solution is used for leaching vanadium slag.
Example 5:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 100g of potassium orthovanadate and 50g of silicic acid, introducing 500ml/min of carbon monoxide, carrying out reduction reaction at 650 ℃, reacting for 2 hours, and cooling the reacted material to 25 ℃ in the atmosphere of carbon monoxide to obtain reduced clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.2g/ml, washing for 1.5h at 30 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 1.5h at 80 ℃ to obtain a vanadium trioxide product;
carbonating the first separated solution at 40 ℃, filtering and separating after the pH value reaches 7.5 to obtain a second solid product and a second separated solution;
returning the second solid product as an auxiliary agent to the step (1), evaporating and concentrating the second separated solution, cooling and crystallizing to obtain potassium carbonate and potassium bicarbonate; the potassium carbonate and the potassium bicarbonate are sold as products or used for roasting vanadium slag.
Example 6:
the embodiment provides a preparation method of vanadium trioxide, which comprises the following steps:
(1) mixing 100g of sodium pyrovanadate, 33g of alumina and 51g of aluminum hydroxide, introducing 700ml/min of natural gas, carrying out reduction reaction at 900 ℃ for 6 hours, and cooling the reacted materials to 30 ℃ in the atmosphere of nitrogen and hydrogen to obtain reduced clinker;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-to-liquid ratio of 0.5g/ml, washing for 1h at 90 ℃, filtering and separating to obtain a first solid product and a first separation solution, and drying the first solid product for 2h at 160 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 30 ℃, filtering and separating after the pH value reaches 8.5 to obtain a second solid product and a second separation solution;
returning the second solid product serving as an auxiliary agent to the step (1), evaporating and concentrating the second separated solution, cooling and crystallizing to obtain sodium carbonate and sodium bicarbonate; the sodium carbonate and sodium bicarbonate are sold as products or used for roasting vanadium slag.
Example 7:
this example provides a method for preparing vanadium trioxide, which is similar to the method in example 2 except that: in the step (1), 100g of sodium orthovanadate and 400g of boric acid are mixed.
Example 8:
this example provides a method for producing vanadium trioxide, which is similar to the method for producing vanadium trioxide in example 6 except that: in the step (1), the reduction reaction is carried out at 950 ℃.
Example 9:
this example provides a method for producing vanadium trioxide, which is similar to the method for producing vanadium trioxide in example 5 except that: in the step (1), reduction reaction is carried out at 600 ℃.
Comparative example 1:
this comparative example provides a process for the preparation of vanadium trioxide, with reference to the preparation of example 4, with the only difference that: no auxiliary agent silicon dioxide is added in the step (1).
The purity of the vanadium trioxide obtained in examples 1 to 9 and comparative example 1, the sodium and/or potassium content in the vanadium trioxide product, and the overall yield of vanadium were measured, and the results are shown in Table 1.
TABLE 1 purity, sodium or potassium content and overall yield of vanadium trioxide obtained in examples 1-9 and comparative example 1
As can be seen from Table 1, the comprehensive yields of vanadium in examples 1-6 are all more than 97%, the purity of vanadium trioxide is more than 96%, and the sodium and/or potassium content in the vanadium trioxide product is less than 0.4%; example 7 increases the addition amount of the auxiliary agent, and the excessive auxiliary agent remains in the vanadium trioxide product, which reduces the vanadium content in the product and affects the product quality; example 8 the reduction temperature is increased, causing partial melting of the materials, difficult separation and affecting the product quality; in the embodiment 9, the reduction temperature is low, vanadium in vanadate can not be completely reduced, and the obtained vanadium trioxide product has poor quality and does not meet the application standard.
In the comparative example 1, no auxiliary agent is added, and vanadium and sodium in vanadate can not be separated, so that the content of sodium in vanadium trioxide exceeds the standard, and the grade is reduced.
It can be seen from the above examples and comparative examples that the method of the present invention adopts a solid phase transformation regulation and control technique, and the vanadium and the alkali metal are separated by adding the auxiliary agent, and the vanadium trioxide is prepared by direct reduction, compared with the prior art, the method has the advantages of simple process flow, mild and safe operation conditions, and low operation cost; in the preparation process, the medium is circulated in a closed loop, no high-ammonia nitrogen and high-salt wastewater is generated, no solid wastewater is discharged, no ammonia gas is discharged, the process is green and clean, and the environment is friendly; according to the preparation method, the addition amount of the auxiliary agent and the temperature of the reduction reaction are further controlled, so that the comprehensive yield of vanadium is more than 97%, the purity of vanadium trioxide is more than 96%, the content of sodium and/or potassium in the vanadium trioxide product is less than 0.4%, the quality meets the preparation requirement of the vanadium alloy product, and the preparation method has a good industrial prospect.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of vanadium trioxide is characterized by comprising the following steps:
(1) mixing vanadate, an auxiliary agent and a reducing agent to perform a reduction reaction to obtain reduced clinker;
(2) and (2) mixing the reduction clinker obtained in the step (1) with water, and carrying out solid-liquid separation to obtain a first solid product and a first separation solution, wherein the first solid product is dried to obtain a vanadium trioxide product.
2. The method according to claim 1, wherein the vanadate in step (1) comprises any one or a combination of at least two of orthovanadate, pyrovanadate or metavanadate;
preferably, the orthovanadate comprises sodium orthovanadate and/or potassium orthovanadate;
preferably, the pyrovanadate comprises sodium pyrovanadate and/or potassium pyrovanadate;
preferably, the metavanadate comprises sodium metavanadate and/or potassium metavanadate;
preferably, the auxiliary agent in step (1) comprises any one or a combination of at least two of an amphoteric compound, a weak acid or an acidic oxide;
preferably, the amphoteric compound comprises aluminum oxide and/or aluminum hydroxide;
preferably, the weak acid comprises silicic acid and/or boric acid;
preferably, the acidic oxide comprises silica and/or phosphorus pentoxide.
3. The production method according to claim 1 or 2, wherein the reducing agent of step (1) includes a solid reducing agent and/or a reducing gas;
preferably, the solid reducing agent comprises carbon;
preferably, the reducing gas comprises any one or a combination of at least two of carbon monoxide, hydrogen, coal gas or natural gas.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the auxiliary agent to vanadate in step (1) is (0.2-3): 1.
5. The method according to any one of claims 1 to 4, wherein the reduction reaction in step (1) is carried out at a reaction temperature of 650 to 900 ℃, preferably 700 to 850 ℃;
preferably, the time of the reduction reaction in the step (1) is 3-5 h.
6. The production method according to any one of claims 1 to 5, wherein the material after the reduction reaction in step (1) is cooled;
preferably, the material after the reduction reaction in the step (1) is cooled in a non-oxidizing atmosphere;
preferably, the non-oxidizing atmosphere comprises a protective gas and/or a reducing gas;
preferably, the protective gas comprises nitrogen and/or argon;
preferably, the reducing gas comprises any one or a combination of at least two of carbon monoxide, hydrogen, coal gas or natural gas.
7. The preparation method according to any one of claims 1 to 6, wherein the solid-to-liquid ratio of the reduction clinker to water in the step (2) is 0.2 to 0.5g/ml, preferably 0.25 to 0.33 g/ml;
preferably, washing is carried out after the mixing in the step (2);
preferably, the washing temperature is 30-90 ℃, and preferably 40-80 ℃;
preferably, the washing time is 1-2 h;
preferably, the drying temperature in the step (2) is 80-160 ℃, and preferably 100-140 ℃;
preferably, the drying time in the step (2) is 1-2 h.
8. The method according to any one of claims 1 to 7, wherein the first separated solution of step (2) is subjected to carbonation treatment;
preferably, the temperature of the carbonation treatment is 20-40 ℃, and preferably 25-30 ℃;
preferably, the pH of the solution after the carbonation treatment is 7-9, and preferably 7.5-8.5.
9. The method according to claim 8, wherein the carbonation treatment is followed by a solid-liquid separation to obtain a second solid product and a second separated solution;
preferably, the second solid product is returned to step (1) as an adjuvant;
preferably, the second separation solution is used for vanadium slag leaching or evaporation concentration, cooling and crystallization to obtain carbonate and/or bicarbonate;
preferably, the carbonate and/or bicarbonate is sold as a product or used in vanadium slag roasting.
10. The method of any one of claims 1 to 9, comprising the steps of:
(1) mixing an auxiliary agent and vanadate with a mass ratio of (0.2-3): 1 with a reducing agent, carrying out a reduction reaction at 650-900 ℃ for 3-5 h, and cooling the reacted material in a non-oxidizing atmosphere to obtain a reduction clinker; the vanadate comprises any one or a combination of at least two of orthovanadate, pyrovanadate or metavanadate, the auxiliary comprises any one or a combination of at least two of amphoteric compounds, weak acids or acidic oxides, the reducing agent comprises any one or a combination of at least two of carbon, carbon monoxide, hydrogen, coal gas or natural gas, and the non-oxidizing gas comprises a protective gas and/or a reducing gas;
(2) mixing the reduction clinker obtained in the step (1) with water according to a solid-liquid ratio of 0.2-0.5 g/ml, washing for 1-2 hours at 30-90 ℃, then carrying out solid-liquid separation to obtain a first solid product and a first separation solution, and drying the first solid product for 1-2 hours at 80-160 ℃ to obtain a vanadium trioxide product;
carrying out carbonation treatment on the first separation solution at the temperature of 20-40 ℃, and carrying out solid-liquid separation after the pH value reaches 7-9 to obtain a second solid product and a second separation solution;
the second solid product is used as an auxiliary agent and returned to the step (1), and the second separation solution is used for leaching vanadium slag or is subjected to evaporation concentration, cooling and crystallization to obtain carbonate and/or bicarbonate; the carbonate and/or bicarbonate is sold as a product or used in vanadium slag roasting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404547.XA CN112408478B (en) | 2020-12-02 | 2020-12-02 | Preparation method of vanadium trioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404547.XA CN112408478B (en) | 2020-12-02 | 2020-12-02 | Preparation method of vanadium trioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112408478A true CN112408478A (en) | 2021-02-26 |
| CN112408478B CN112408478B (en) | 2022-03-15 |
Family
ID=74830090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011404547.XA Active CN112408478B (en) | 2020-12-02 | 2020-12-02 | Preparation method of vanadium trioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112408478B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395601A (en) * | 1991-04-09 | 1995-03-07 | Qi-Jiang Situ | Re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues |
| CN103101976A (en) * | 2013-02-19 | 2013-05-15 | 中国科学院过程工程研究所 | Preparation method of vanadium trioxide powder |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| CN106629847A (en) * | 2017-01-17 | 2017-05-10 | 中南大学 | Method for preparing vanadium trioxide from sodium-vanadate salt |
| CN107662946A (en) * | 2017-08-11 | 2018-02-06 | 攀枝花学院 | The preparation method of vanadium trioxide |
-
2020
- 2020-12-02 CN CN202011404547.XA patent/CN112408478B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395601A (en) * | 1991-04-09 | 1995-03-07 | Qi-Jiang Situ | Re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues |
| CN103101976A (en) * | 2013-02-19 | 2013-05-15 | 中国科学院过程工程研究所 | Preparation method of vanadium trioxide powder |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| CN106629847A (en) * | 2017-01-17 | 2017-05-10 | 中南大学 | Method for preparing vanadium trioxide from sodium-vanadate salt |
| CN107662946A (en) * | 2017-08-11 | 2018-02-06 | 攀枝花学院 | The preparation method of vanadium trioxide |
Non-Patent Citations (1)
| Title |
|---|
| 纪柱: "铬渣的物相组成及其对铬渣解毒和综合利用的影响", 《化工环保》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112408478B (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106848474B (en) | Method for recovering positive electrode material and lithium carbonate from lithium ion battery positive electrode waste material | |
| CN102603000B (en) | Process for preparing high-purity vanadium pentoxide by adopting ammonium metavanadate as raw material | |
| CN111994952A (en) | Method for preparing high-purity vanadium pentoxide by vacuum sublimation of metallurgical-grade vanadium pentoxide | |
| CN107117654B (en) | A method of vanadium dioxide is prepared from containing vanadium solution | |
| CN114318008B (en) | Method for extracting lithium by secondary reverse leaching of spodumene with nitric acid | |
| CN110683580B (en) | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination | |
| CN108642271B (en) | Novel method for producing vanadium dioxide from vanadium-containing shale without ammonium vanadium precipitation | |
| CN110898794A (en) | Preparation method of lithium ion sieve | |
| CN108264086B (en) | Method for preparing vanadium pentoxide by ball milling calcification-ammonification of vanadium-containing raw material | |
| CN114231758A (en) | Vanadium pentoxide and ammonium-free preparation method and application thereof | |
| CN106629847A (en) | Method for preparing vanadium trioxide from sodium-vanadate salt | |
| CN110331297B (en) | Method for preparing vanadium pentoxide from vanadium slag in short process | |
| CN112408478B (en) | Preparation method of vanadium trioxide | |
| CN110357156B (en) | Method for preparing vanadium dioxide from vanadium slag in short process | |
| CN115108584B (en) | Method for efficiently preparing vanadium pentoxide and calcium carbonate by utilizing calcium vanadate | |
| CN116404220A (en) | Method for preparing high-concentration vanadium electrolyte by vanadate crystallization purification-chemical reduction | |
| CN115286019A (en) | Method for producing high-purity lithium carbonate from spodumene | |
| CN110723747B (en) | Method for recovering and preparing high-quality zinc oxide from zinc waste | |
| CN111186851B (en) | Method for preparing modified aluminum-based catalyst by recycling electric dust collection powder of fluidized bed roaster | |
| CN114292180A (en) | Method for preparing high-purity vanadyl oxalate by extraction method | |
| CN112266017A (en) | Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste | |
| CN115057474B (en) | Method for medium internal circulation in process of preparing ammonium metavanadate from calcium vanadate | |
| CN115621515B (en) | Method for preparing vanadium electrolyte for all-vanadium redox flow battery from vanadium-containing raw material in short process and vanadium electrolyte | |
| CN114436330B (en) | Preparation method of alpha-hydroxy chromium oxide | |
| CN115259223B (en) | Method for preparing ammonium metavanadate from calcium vanadate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |