CN114231758B - Vanadium pentoxide, and ammonium-free preparation method and application thereof - Google Patents
Vanadium pentoxide, and ammonium-free preparation method and application thereof Download PDFInfo
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- CN114231758B CN114231758B CN202111497832.5A CN202111497832A CN114231758B CN 114231758 B CN114231758 B CN 114231758B CN 202111497832 A CN202111497832 A CN 202111497832A CN 114231758 B CN114231758 B CN 114231758B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention provides vanadium pentoxide, an ammonium-free preparation method and application thereof. The ammonium-free preparation method of vanadium pentoxide comprises the following steps: step 1, sodium roasting, namely uniformly mixing sodium carbonate and a vanadium-containing raw material, putting the mixture into a kiln, oxidizing and calcining at a high temperature, and converting vanadium into water-soluble sodium vanadate; step 2, leaching and filtering, namely dissolving the material obtained by calcining in the step 1 in water, and filtering to obtain sodium vanadate leaching solution and waste residues; step 3, adding acid to remove impurities; adding a reducing agent, and reducing vanadium to tetravalent to obtain a mixed solution of tetravalent vanadium and sodium sulfate; step 4, extracting-back extracting vanadium, and performing a liquid-liquid extraction-back extraction method by using an extracting agent to obtain vanadyl sulfate solution and raffinate containing sodium sulfate; step 5, crystallizing to obtain vanadyl sulfate crystals; and 6, calcining and decomposing vanadyl sulfate to obtain vanadium pentoxide. The invention has low production cost, and the vanadium pentoxide product has smaller granularity and larger specific surface area.
Description
Technical Field
The invention relates to a vanadium pentoxide production method technology, in particular to vanadium pentoxide, an ammonium-free preparation method and application thereof.
Background
At present, vanadium titano-magnetite is a main vanadium resource source, and the original content of the vanadium titano-magnetite is lower than 1%. Refining iron, enriching vanadium in slag, and concentrating V 2 O 5 The content is improved to more than 8 percent, and the vanadium-free alloy can be used as a source of vanadium to enter the vanadium chemical industry. The traditional vanadium extraction method comprises the steps of sodium roasting, neutralization and impurity removal, ammonium salt precipitation to obtain ammonium vanadate, and high-temperature calcination or melt casting to obtain vanadium pentoxide or sheet vanadium. In this process, since ammonium salts are used, a large amount of wastewater containing ammonium and sodium is generated, and it is necessary to deaminize high Wen Jiajian and then dry to obtain sodium salts to prepare sodium sulfate crystals. When steaming ammonium, a large amount of caustic soda flakes and steam are consumed, the cost is high, and the environmental pollution is serious. The sodium sulfate crystal has limited application and cannot be consumed in time, and the problem that the vanadium plant is stored mainly at present is solved, and leakage occurs when rainwater falls. It is therefore desirable to find an alternative method for vanadium extraction to reduce cost and simplify the process.
Vanadium oxides are important catalysts in the organic synthesis industry, for example, the production process of sulfuric acid, the production of maleic anhydride and the synthesis of adipic acid, and different vanadium oxides are used as catalysts.
Vanadium oxide used as a catalyst is required to have a small particle size and a large specific surface area in order to maximize the catalytic effect.
The traditional vanadium oxide production method needs ammonium vanadate precipitation and calcination, is an ammonium-containing chemical process, has higher production cost, needs deamination treatment of the generated wastewater, and also has the problems of ammonia pollution and emission in the production process.
Therefore, a low-emission short-process vanadium pentoxide production method is urgently needed, and the effect of green and high-efficiency vanadium extraction is achieved.
Disclosure of Invention
Aiming at the problems that the traditional vanadium oxide production method needs ammonium vanadate precipitation and calcination, is a chemical process containing ammonium, has higher production cost, needs deamination treatment of the generated wastewater and has ammonia pollution and emission in the production process, the invention provides an ammonium-free vanadium pentoxide preparation method, which has low production cost and smaller granularity and larger specific surface area.
In order to achieve the above purpose, the invention adopts the following technical scheme: an ammonium-free preparation method of vanadium pentoxide comprises the following steps:
step 1, sodium roasting
Uniformly mixing sodium carbonate and a vanadium-containing raw material (such as crushed steel slag), putting into a kiln, oxidizing and calcining at high temperature, and converting vanadium into water-soluble sodium vanadate;
step 2, leaching and filtering
Dissolving the material obtained by calcining in the step 1 in water, and filtering to obtain sodium vanadate leaching solution and waste residues;
step 3, acidizing reduction
Adding acid to remove impurities, adding a stabilizer into the solution, and reducing vanadium to tetravalent to obtain a mixed solution of tetravalent vanadium (such as vanadyl sulfate) and sodium sulfate;
step 4, extracting-back extracting vanadium
Extracting with extractant to obtain vanadyl sulfate solution and raffinate containing sodium sulfate;
step 5, crystallizing to obtain vanadyl sulfate crystals;
and 6, calcining and decomposing vanadyl sulfate crystals to obtain vanadium pentoxide.
Further, the vanadium-containing raw material is one or more of stone coal, vanadium slag and vanadium titano-magnetite; the granularity of the vanadium-containing raw material is 200 um-1 mm.
Further, sodium carbonate in step 1 and vanadium (V 2 O 5 ) The mass ratio of (2) to (4) is 1-5:1, preferably 2-4:1.
Further, the conditions of the high-temperature oxidation calcination in the step 1 are 700-1000 ℃ and the calcination time is 1-30 h. The preferable conditions of high-temperature oxidation calcination are 800-900 ℃ and air atmosphere for 6-12 hours.
Further, the leaching condition in the step 2 is that the liquid-solid ratio is 1-5:1, the temperature is 60-100 ℃, and the time is 1-24 hours. The preferred leaching condition is that the liquid-solid ratio is 3-5:1, the temperature is 80-100 ℃ and the time is 12-24 hours.
Further, in the step 3, acid is added for removing impurities, the acid is one or a mixture of sulfuric acid, phosphoric acid and hydrochloric acid, the final pH value is 1-4, preferably 1.5-3, and the stirring reaction time is 0.5-10 h, preferably 5-10 h.
Further, the stabilizer in the step 3 is one or more of phosphoric acid, monohydrogen phosphate, dihydrogen phosphate, metaphosphate and pyrophosphates. The addition of the stabilizer can stabilize the vanadium-containing aqueous solution and prevent precipitation from occurring in the extraction process to cause a third phase;
further, the reduction in the step 3 is electrolytic current reduction or adding a reducing agent, wherein the reducing agent is sulfur dioxide, glucose, sucrose, citric acid, oxalic acid, iron powder, aluminum powder and V 2 O 3 Mixing of one or more of vanadium sulphate or hydrazine hydrate and VC.
Further, the crystallization method in step 5 is cooling crystallization or evaporation crystallization.
Further, the crystallization mother liquor of step 5 is returned to step 2 for leaching.
Further, sulfur dioxide and sulfur trioxide gas which are byproducts generated by calcining and decomposing in the step 6 are introduced into the step 3 to replace sulfuric acid and a reducing agent;
the invention also discloses vanadium pentoxide, which is prepared by the method. The vanadium pentoxide prepared by the method has smaller granularity and larger specific surface area.
The invention also discloses an application of the ammonium-free preparation method of the vanadium pentoxide in the field of producing the vanadium pentoxide by directly extracting vanadium from the vanadium-containing raw material.
The invention relates to a working principle of a preparation method of ammonium-free vanadium pentoxide:
(1) The invention adopts a double-circulation process, wherein the double circulation means that sulfur and sodium salt circulate in the vanadium extraction process, and the vanadium extraction process is not increased.
(2) The acidification and reduction process can remove main impurities in the solution to obtain a purified vanadyl sulfate/sodium sulfate solution;
(3) The invention provides a stable mode of the extraction process, which can prevent the occurrence of a third phase in the extraction process and is beneficial to the separation of two phases;
(4) The reduction-liquid extraction process can prepare vanadyl sulfate solution in one step, and further crystallize to obtain vanadyl sulfate;
(5) The product of the invention comprises vanadium pentoxide, sulfur dioxide and sulfur trioxide, wherein by-product sulfur dioxide and sulfur trioxide gas can be used for acidizing reduction of the solution;
compared with the prior art, the vanadium pentoxide, the ammonium-free preparation method and the application thereof have the following advantages:
1) The invention adopts a liquid-liquid extraction method to replace an ammonium salt precipitation process for removing impurities, reduces the ammonium salt consumption and the subsequent ammonium removal operation, and obviously reduces the cost and the environmental pollution;
2) According to the invention, the vanadyl sulfate is prepared by directly extracting vanadium from raw material leaching liquid, and then the vanadyl sulfate crystal is obtained through crystallization, so that the production flow of the electrolyte is greatly simplified, the cost is obviously reduced, and the production time is shortened;
3) The invention adopts a sulfur oxide circulating system, thereby effectively reducing the sulfur dioxide emission.
Drawings
FIG. 1 is a reaction scheme;
FIG. 2 is an SEM image of vanadium pentoxide obtained in example 1;
FIG. 3 is a schematic diagram of a conventional V obtained by calcining AMV 2 O 5 SEM images of (a);
fig. 4 is an XRD pattern of vanadium pentoxide.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses an ammonium-free preparation method of vanadium pentoxide, which comprises the following steps as shown in fig. 1:
1. the ratio of sodium carbonate to vanadium slag (V8.3%) is 1:1, the air atmosphere is adopted, the calcination is carried out for 12 hours at 850 ℃, and the calcined product is clinker;
2. leaching the clinker with water according to a liquid-solid ratio of 4:1 to obtain vanadium slag leaching solution containing V31 g/L;
3. adding sulfuric acid to acidify until the pH value is 2, maintaining the temperature at 80 ℃, continuously stirring, and introducing sulfur dioxide until the solution turns to be pure blue;
4. by P 2 0 4 Adjusting the pH value of sodium hydroxide serving as an extractant, and extracting vanadium into an organic phase; repeatedly extracting with dilute sulfuric acid as back extractant until vanadium concentration reaches 50g/L;
5. evaporating and crystallizing to obtain vanadyl sulfate crystals, returning residual mother liquor to the step 4, and mixing with the newly obtained vanadyl sulfate solution;
6. calcining for 4 hours at 600 ℃ in oxygen atmosphere to obtain vanadium pentoxide powder, and returning tail gas to the step 3 for acidification and vanadium reduction.
V 2 O 5 BET is 11 square meters/g, V obtained by AMV calcination 2 O 5 BET is 4 square meters/g, SEM is shown in figure 2, and comparison of figure 2 and figure 3 shows that the vanadium pentoxide prepared by the method provided by the patent has smaller granularity, larger specific surface area and XRD is shown in figure 4.
Example 2
The embodiment discloses an ammonium-free preparation method of vanadium pentoxide, which comprises the following steps:
1. the ratio of sodium carbonate to petroleum fly ash (V16.6%) is 2:1, the air atmosphere is adopted, the calcination is carried out for 6 hours at 900 ℃, and the calcined product is clinker;
2. leaching the clinker with water according to a liquid-solid ratio of 4:1 to obtain vanadium slag leaching solution containing V40 g/L;
3. adding sulfuric acid to acidify until the pH value is 1.5, maintaining the temperature at 90 ℃, continuously stirring, adding 1/16 of citric acid according to the vanadium content, and continuously stirring for reaction until the solution turns into pure blue;
4. by P 2 0 4 Adjusting the pH value of sodium hydroxide serving as an extractant, and extracting vanadium into an organic phase; repeatedly extracting with dilute sulfuric acid as back extractant until vanadium concentration reaches 150g/L;
5. cooling and crystallizing to obtain vanadyl sulfate crystals, returning residual mother liquor to the step 4, adding sulfuric acid and using the sulfuric acid for back extraction;
6. calcining for 6 hours at 550 ℃ in oxygen atmosphere to obtain vanadium pentoxide powder, and returning tail gas to the step 3 for acidification and vanadium reduction.
Example 3
The embodiment discloses an ammonium-free preparation method of vanadium pentoxide, which comprises the following steps:
1. the ratio of sodium carbonate to petroleum gas coking slag (V3.2%) is 5:1, the air atmosphere is adopted, the calcination is carried out for 24 hours at 700 ℃, and the calcined product is clinker;
2. leaching the clinker with water according to a liquid-solid ratio of 2:1 to obtain vanadium slag leaching solution containing V70 g/L;
3. acidifying with sulfuric acid until pH value is 2, maintaining the temperature at 90 ℃, continuously stirring, adding zinc powder according to the mass of vanadium, continuously stirring for reaction until the solution turns to be pure blue, and filtering to remove residual zinc powder;
4. by P 2 0 4 Adjusting the pH value of sodium hydroxide serving as an extractant, and extracting vanadium into an organic phase; repeatedly extracting with dilute sulfuric acid as back extractant until vanadium concentration reaches 100g/L;
5. evaporating and crystallizing to obtain vanadyl sulfate crystals, and returning residual mother liquor to the step 4;
6. calcining in oxygen atmosphere to obtain vanadium pentoxide powder, and returning tail gas to the step 3 for acidification and vanadium reduction.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. The ammonium-free preparation method of vanadium pentoxide is characterized by comprising the following steps of:
step 1, sodium roasting
Uniformly mixing sodium carbonate and a vanadium-containing raw material, putting the mixture into a kiln, oxidizing and calcining the mixture at a high temperature, and converting vanadium into water-soluble sodium vanadate;
step 2, leaching and filtering
Dissolving the material obtained by calcining in the step 1 in water, and filtering to obtain sodium vanadate leaching solution and waste residues;
step 3, acidizing reduction
Adding acid to remove impurities, adding a stabilizer into the solution, and reducing vanadium to tetravalent to obtain a mixed solution of tetravalent vanadium and sodium sulfate; adding acid to remove impurities, wherein the acid is one or more of sulfuric acid, phosphoric acid and hydrochloric acid, the pH value of the end point is 1-4, and the stirring reaction time is 0.5-10 h; the stabilizer is one or more of phosphoric acid, monohydrogen phosphate, dihydrogen phosphate, metaphosphate and pyrophosphates;
step 4, extracting-back extracting vanadium
Extracting with extractant to obtain vanadyl sulfate solution and raffinate containing sodium sulfate;
step 5, crystallizing to obtain vanadyl sulfate crystals, and returning crystallization mother liquor to the step 2 for leaching;
and 6, calcining and decomposing vanadyl sulfate crystals to obtain vanadium pentoxide, and introducing sulfur dioxide and sulfur trioxide gas which are byproducts generated by calcining and decomposing into the step 3 to replace sulfuric acid and a reducing agent.
2. The method for preparing vanadium pentoxide without ammonium according to claim 1, wherein the vanadium-containing raw material is a mixture of one or more of stone coal, vanadium slag and vanadium titano-magnetite; the granularity of the vanadium-containing raw material is 200 um-1 mm.
3. The ammonium-free preparation method of vanadium pentoxide according to claim 1, wherein the mass ratio of sodium carbonate to vanadium in the vanadium-containing raw material in the step 1 is 1-5:1.
4. The method for preparing vanadium pentoxide without ammonium according to claim 1, wherein the condition of high-temperature oxidation calcination in step 1 is 700-1000 ℃ and calcination time is 1-30 h.
5. Vanadium pentoxide, characterized in that it is prepared by the process according to any one of claims 1 to 4.
6. Use of an ammonium-free preparation method of vanadium pentoxide according to any one of claims 1-4 in the field of vanadium pentoxide production by direct vanadium extraction of vanadium-containing raw materials.
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| CN107557598B (en) * | 2017-05-25 | 2019-04-30 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| CN110395766B (en) * | 2019-08-26 | 2022-04-15 | 广东省稀有金属研究所 | Preparation method of solid vanadyl sulfate |
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