CN103626230A - Method for preparing vanadyl sulfate - Google Patents
Method for preparing vanadyl sulfate Download PDFInfo
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- CN103626230A CN103626230A CN201310421918.9A CN201310421918A CN103626230A CN 103626230 A CN103626230 A CN 103626230A CN 201310421918 A CN201310421918 A CN 201310421918A CN 103626230 A CN103626230 A CN 103626230A
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- oxalic acid
- vanadylic sulfate
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Abstract
The invention provides a method for preparing vanadyl sulfate. The method comprises the following steps: dissolving vanadium pentoxide into an oxalic acid solution so as to obtain a vanadyl oxalate solution, adding sulfuric acid into the vanadyl oxalate solution, uniformly stirring so as to obtain a mixture liquid, and roasting so as to obtain vanadyl sulfate. The method has the advantages that the dissolution velocity of vanadium pentoxide is increased, the addition amount of sulfuric acid is reduced, and vanadyl sulfate powder with high purity (for example, the purity is no less than 99.0wt%) can be prepared.
Description
Technical field
The present invention relates to vanadylic sulfate production technical field, specifically, relate to a kind of method of preparing vanadylic sulfate.
Background technology
Conventionally, vanadylic sulfate is as a kind of common Chemicals, be mainly used in the mordant of fabric, catalyzer, the electrolytic solution of reductive agent and vanadium cell etc., it has the production technique of comparative maturity, the general sulfuric acid that adopts activates Vanadium Pentoxide in FLAKES, then passes into sulfur dioxide gas reduction, and 5 valency vanadium are reduced to 4 valency vanadium, obtain vanadylic sulfate solution, SO in this solution
4 2-with V
4+mol ratio be greater than 1, strongly-acid makes the method be difficult to directly to obtain vanadylic sulfate solid, its purity is difficult to surpass 97%.Unnecessary SO
4 2-the product that the excess sulfuric acid of using while being mainly derived from activation Vanadium Pentoxide in FLAKES and sulfur dioxide gas reduction obtain.
The patent documentation that publication number is CN102476829A provides a kind of preparation method of vanadylic sulfate, it is under 9～10.5 condition that the method is included in pH value, by vanadium extraction leach liquor and water-soluble Ca salt carry out first contact after, through solid-liquid separation, obtain solid, described solid is made after hydrous slurry and to be carried out second with sulfuric acid and contact that to make the pH value of this slip be 1.5～3, the slip that is 1.5～3 by this pH value carries out the 3rd with sulfur dioxide gas again and contacts, and the product after the 3rd contact is obtained to the solution of vanadylic sulfate through solid-liquid separation.
Publication number be CN101920994A Patent Application Publication a kind of method of preparing vanadylic sulfate, the method comprises the following steps: by ammonium meta-vanadate in airtight reactor with the temperature calcining of 540 ℃～600 ℃; In the product obtaining to calcining, add sulfuric acid and pass into SO
2gas, heats infusion; Make to heat the solution crystallization obtaining after infusion, thereby obtain vanadylic sulfate.
The patent documentation that publication number is CN101648727A provides a kind of preparation method of vanadylic sulfate, wherein, the method comprises that the hydrochloric acid that Vanadium Pentoxide in FLAKES and concentration are at least to 30 % by weight contacts, and the solution of gained is used with the extraction agent extraction chlorine of the immiscible extraction chlorine of water and obtained water; Water is contacted with sulphur aqueous acid at 70～80 ℃, and in Vanadium Pentoxide in FLAKES, the mol ratio of sulfuric acid and water is 2: 1～4: 1; With pH value conditioning agent, regulating pH value is afterwards 6～7, this pH value conditioning agent is difficult water-soluble and can react and generate the compound of the vitriol be insoluble in water with sulfuric acid, solid-liquid separation obtains the liquid that contains vanadylic sulfate, and the water of removing in this liquid obtains vanadylic sulfate.Adopt the purity of vanadylic sulfate prepared by method of the present invention higher, purity is all higher than 95%, and adopt the purity of vanadylic sulfate prepared by comparative example, is only 81%.
Publication number is the preparation method that the patent documentation of CN1491898A discloses a kind of vanadylic sulfate, and this preparation method comprises that a. adds V in sulfuric acid
2o
3and V
2o
5; B. filter, by filtrate evaporative crystallization; C. slough crystal water, obtain VOSO
4light blue powder.Compare with existing operational path, omitted heating for dissolving, cooling dilution, the steps such as reduction, reaction conditions is gentle, and technique is simple, cost, constant product quality.The filtrate obtaining from step a, b can be directly as the raw material of preparing electrolyte of vanadium redox battery.
The patent documentation that publication number is CN103193268A provides a kind of vanadylic sulfate preparation method for vanadium cell, comprising: (1) is used sulfuric acid to carry out heat-activated vanadium pentoxide powder, obtains the solution containing Vanadium Pentoxide in FLAKES; (2) solution of step (1) gained is carried out to cooling and dilution; (3) in the solution of step (2) gained, add reductive agent, vanadium ion is restored; (4) mixing solutions after reduction is filtered under normal pressure, then dewater and drying treatment, obtain vanadylic sulfate.
Publication number is the preparation method that the patent documentation of CN102951680A discloses a kind of vanadylic sulfate, and the method comprises the steps: that (1) use sulfuric acid dissolution Vanadium Pentoxide in FLAKES, obtains activated solution; (2) described activated solution is contacted with reductive agent, so that the pentavalent vanadium in described activated solution is reduced to tetravalence vanadium, obtain reduzate; (3) with alkali, adjust the pH value of described reduzate, so that the tetravalence vanadium in described reduzate is separated out as precipitation; (4) with carrying out crystallization after precipitation described in sulfuric acid dissolution, obtain vanadylic sulfate solid, with respect to the tetravalence vanadium of 1 mole in described precipitation, the consumption of described sulfuric acid is 0.9～1.1 mole.In the vanadylic sulfate product of preparing by the method, the contents on dry basis of vanadylic sulfate can reach 97 % by weight.
Publication number is the preparation method that the patent documentation of CN101613127A discloses a kind of vanadylic sulfate, and its technique mainly comprises: a) in sulfuric acid, add Vanadium Pentoxide in FLAKES; B) add diamine or azanol; C) evaporative crystallization obtains blue VOSO.xH
2o crystal.This operational path is compared with existing operational path, has reduced heating for dissolving, cooling dilution, the steps such as electrolysis.
Summary of the invention
The object of the invention is to solve at least one in the above-mentioned deficiency of prior art.
For example, thus one of object of the present invention is to provide a kind of method of preparing vanadylic sulfate that can avoid reactivation process to raise the efficiency.
Another object of the present invention is to provide a kind of method of preparing powdered form high-purity sulphuric acid vanadyl.
The invention provides a kind of method of preparing vanadylic sulfate.Said method comprising the steps of: Vanadium Pentoxide in FLAKES is dissolved in oxalic acid solution, obtains oxalic acid vanadyl solution; To oxalic acid vanadyl solution, add sulfuric acid, stir, obtain mixed solution; Roasting, obtains vanadylic sulfate.
Compared with prior art, beneficial effect of the present invention comprises: the dissolution rate that can improve Vanadium Pentoxide in FLAKES; Reduced the add-on of sulfuric acid; Can make the vanadylic sulfate powder of high purity (for example, purity is not less than 99.0wt%, and purity is not less than 99.5wt% even).
Embodiment
Hereinafter, in connection with exemplary embodiment, describe the method for preparing vanadylic sulfate of the present invention in detail.
Contriver is through repetition test and analysis; find that traditional vanadylic sulfate preparation technology conventionally need to join sulfuric acid Vanadium Pentoxide in FLAKES or Vanadium Pentoxide in FLAKES be joined in sulfuric acid and activated; and then add suitable reductive agent to reduce; 5 valency vanadium are reduced to 4 valencys, so traditional vanadylic sulfate preparation technology faces an inevitable difficult problem, reactivation process is very slow; under the certain condition of temperature; accelerate activating velocity, need to increase the consumption of sulfuric acid, especially use SO
2in the situation that gas reduces, make SO in solution
4 2-with V
4+mol ratio be greater than 1, this causes again in the process of later stage evaporative crystallization, is difficult to remove moisture completely and obtains dry vanadylic sulfate powder.For above-mentioned discovery, contriver provides the method for preparing vanadylic sulfate of the present invention.
The method of preparing vanadylic sulfate according to the present invention comprises the following steps: Vanadium Pentoxide in FLAKES is dissolved in oxalic acid solution, obtains oxalic acid vanadyl solution; To oxalic acid vanadyl solution, add sulfuric acid, stir, obtain mixed solution; Roasting, obtains vanadylic sulfate.The vanadylic sulfate that the present invention makes is Powdered.In the method for the invention, after oxalic acid is mixed with high purity vanadic anhydride, owing to there is redox reaction between the two, cause Vanadium Pentoxide in FLAKES to dissolve fast, thus longer reactivation process while having avoided sulfuric acid dissolution Vanadium Pentoxide in FLAKES.
In a preferred illustrative embodiment who prepares vanadylic sulfate method of the present invention, the mol ratio that the step that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution is controlled oxalic acid solution mesoxalic acid and Vanadium Pentoxide in FLAKES is 3～3.45:1.If the mol ratio of oxalic acid solution mesoxalic acid and Vanadium Pentoxide in FLAKES is controlled as being less than 3:1, can not be by Vanadium Pentoxide in FLAKES Restore All; If the mol ratio of oxalic acid solution mesoxalic acid and Vanadium Pentoxide in FLAKES is controlled as being greater than 3.45:1, oxalic acid is excessive too many, may cause reduction, and this not only increases the ratio of trivalent vanadium, also can increase the difficulty of subsequent disposal oxalic acid.And adding the step of sulfuric acid can control sulfuric acid to oxalic acid vanadyl solution is 1.95～2.05:1 with the mol ratio that is dissolved in the Vanadium Pentoxide in FLAKES in oxalic acid solution.
In the method for the invention, the mol ratio of controlling oxalic acid solution mesoxalic acid and Vanadium Pentoxide in FLAKES in the step that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution is 3～3.45:1, and can control sulfuric acid and be dissolved in the situation that the mol ratio of the Vanadium Pentoxide in FLAKES in oxalic acid solution is 1.95～2.05:1 add the step of sulfuric acid to oxalic acid vanadyl solution, can greatly improve the purity of the vanadylic sulfate making, for example, can obtain purity and be not less than 99.0% Powdered vanadylic sulfate, obtain even purity and be not less than 99.5% Powdered vanadylic sulfate.
In a preferred illustrative embodiment who prepares vanadylic sulfate method of the present invention, when the step that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution also can be included in and dissolve, carry out water-bath, and to control bath temperature be 50～95 ℃.Because this reaction has gas, emit, thus for fear of violent splash, so Temperature Setting for not higher than 95 ℃; Experiment shows, bath temperature below 50 ℃ time, reacts slower, for fast reaction speed, reduces the reaction times, and lowest temperature is set as to 50 ℃.At this, preferably in exemplary embodiment, the reaction times that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution step can be 15～30min.
In a preferred illustrative embodiment who prepares vanadylic sulfate method of the present invention, maturing temperature can be 220～260 ℃, and roasting time can be 30～60min.Temperature range roasting 30～60min at 220～260 ℃, can remove the oxalic acid in evaporate totally effectively, has guaranteed the higher-grade of vanadylic sulfate powder.
In a preferred illustrative embodiment who prepares vanadylic sulfate method of the present invention, in the situation that the grade of the oxalic acid that Vanadium Pentoxide in FLAKES and oxalic acid solution are used is not less than 99.5%, the grade of the vanadylic sulfate making is not less than 99.0%.
In another exemplary embodiment of the present invention, the method for preparing vanadylic sulfate can realize in the following manner:
By high-purity vanadium pentoxide (for example, grade is not less than 99.5wt%) by highly purified oxalic acid (be for example dissolved in, grade is not less than 99.5wt%) and the oxalic acid solution that forms of pure water in, for example, through after a while (, more than 15min) water-bath (for example, bath temperature can be 50～95 ℃) reaction, obtain oxalic acid vanadyl solution; Then, in oxalic acid vanadyl solution, add appropriate sulfuric acid, stir, pour into and in crucible, be placed in again process furnace and (for example carry out high-temperature roasting, maturing temperature can be 220～260 ℃, and roasting time can be for more than 30min), remove residual oxalic acid, obtain high-purity sulfuric acid vanadyl (for example, grade is not less than 99.5wt%).
Wherein, the mol ratio of oxalic acid and high purity vanadic anhydride is 3～3.45:1, is preferably 3:1; Sulfuric acid is 1.95～2.05:1 with the mol ratio that is dissolved in the Vanadium Pentoxide in FLAKES in oxalic acid, is preferably 2:1.
Concrete example below is only described and is prepared according to an exemplary embodiment of the present invention vanadylic sulfate method for illustrating property object.
Example 1
Prepare the oxalic acid (H that grade is not less than 99.5wt%
2c
2o
42H
2o) 37.8g, grade are not less than the Vanadium Pentoxide in FLAKES 18.2g of 99.5wt%, sulfuric acid 26.9ml that mass concentration is 50% and appropriate pure water.
Oxalic acid is joined in 200ml pure water and dissolves and be prepared into solution, high-purity vanadium pentoxide is dissolved in oxalic acid solution, carry out water-bath, 50 ℃ of bath temperatures, reaction times 30min.Question response finishes, and then adds the sulfuric acid of preparation, stirs, and pours crucible into, then is placed in process furnace and carries out roasting, and the temperature of roasting is 220 ℃, roasting time 60min.The sample obtaining is jade-green vanadylic sulfate powder.After testing, the sample purity obtaining is 99.2%, and the vanadium yield of technique is 99.7%.
Example 2
Prepare the oxalic acid (H that grade is not less than 99.5wt%
2c
2o
42H
2o) 18.9g, grade are not less than the Vanadium Pentoxide in FLAKES 9.1g of 99.5wt%, sulfuric acid 5.4ml that mass concentration is 98% and appropriate pure water.
Oxalic acid is joined in 150ml pure water and dissolves and be prepared into solution, high-purity vanadium pentoxide is dissolved in oxalic acid solution, carry out water-bath, 95 ℃ of bath temperatures, reaction times 15min.Question response finishes, and then adds the sulfuric acid of preparation, stirs, and pours crucible into, then is placed in process furnace and carries out roasting, and the temperature of roasting is 260 ℃, roasting time 30min.The sample obtaining is jade-green vanadylic sulfate powder.After testing, the sample purity obtaining is 99.6%, and the vanadium yield of technique is 99.3%.
Example 3
Prepare the oxalic acid (H that grade is not less than 99.5wt%
2c
2o
42H
2o) 56.7g, grade are not less than the Vanadium Pentoxide in FLAKES 27.3g of 99.5wt%, sulfuric acid 16.5ml that mass concentration is 98% and appropriate pure water.
Oxalic acid is joined in 200ml pure water and dissolves and be prepared into solution, high-purity vanadium pentoxide is dissolved in oxalic acid solution, carry out water-bath, 85 ℃ of bath temperatures, reaction times 20min.Question response finishes, and then adds the sulfuric acid of preparation, stirs, and pours crucible into, then is placed in process furnace and carries out roasting, and the temperature of roasting is 240 ℃, roasting time 40min.The sample obtaining is jade-green vanadylic sulfate powder.After testing, the sample purity obtaining is 99.1%, and the vanadium yield of technique is 99.5%.
Example 4
Prepare the oxalic acid (H that grade is not less than 99.5wt%
2c
2o
42H
2o) 75.6g, grade are not less than the Vanadium Pentoxide in FLAKES 36.4g of 99.5wt%, sulfuric acid 21.4ml that mass concentration is 98% and appropriate pure water.
Oxalic acid is joined in 200ml pure water and dissolves and be prepared into solution, high-purity vanadium pentoxide is dissolved in oxalic acid solution, carry out water-bath, 70 ℃ of bath temperatures, reaction times 25min.Question response finishes, and then adds the sulfuric acid of preparation, stirs, and pours crucible into, then is placed in process furnace and carries out roasting, and the temperature of roasting is 230 ℃, roasting time 50min.The sample obtaining is jade-green vanadylic sulfate powder.After testing, the sample purity obtaining is 99.7%, and the vanadium yield of technique is 99.2%.
In sum, method of the present invention is first by high purity vanadic anhydride and oxalic acid hybrid reaction, and then add the method for sulfuric acid, improved greatly the dissolution rate of Vanadium Pentoxide in FLAKES, reduced the add-on of sulfuric acid, making evaporation obtain high-purity sulphuric acid vanadyl powder becomes corollary, that is to say, method of the present invention has improved grade and the preparation efficiency of vanadylic sulfate.In addition, the high-temperature roasting method that the present invention adopts removes unnecessary oxalic acid, can guarantee to the full extent the recovery rate of vanadylic sulfate product, avoids vanadium loss, has good economic benefit and application prospect.
Although described the present invention in conjunction with exemplary embodiment above, those of ordinary skills should be clear, in the situation that do not depart from the spirit and scope of claim, can carry out various modifications to above-described embodiment.
Claims (8)
1. a method of preparing vanadylic sulfate, is characterized in that, said method comprising the steps of:
Vanadium Pentoxide in FLAKES is dissolved in oxalic acid solution, obtains oxalic acid vanadyl solution;
To oxalic acid vanadyl solution, add sulfuric acid, stir, obtain mixed solution;
Roasting, obtains vanadylic sulfate.
2. the method for preparing vanadylic sulfate according to claim 1, is characterized in that, the mol ratio that the described step that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution is controlled oxalic acid solution mesoxalic acid and Vanadium Pentoxide in FLAKES is 3～3.45:1.
3. the method for preparing vanadylic sulfate according to claim 2, is characterized in that, described to oxalic acid vanadyl solution, to add the step of sulfuric acid to control sulfuric acid be 1.95～2.05:1 with the mol ratio that is dissolved in the Vanadium Pentoxide in FLAKES in oxalic acid solution.
4. the method for preparing vanadylic sulfate according to claim 3, is characterized in that, the grade of the oxalic acid that described Vanadium Pentoxide in FLAKES and oxalic acid solution are used is not less than 99.5%, and the grade of described vanadylic sulfate is not less than 99.0%.
5. the method for preparing vanadylic sulfate according to claim 1, is characterized in that, the described step that Vanadium Pentoxide in FLAKES is dissolved in to oxalic acid solution is also included in while dissolving carries out water-bath, and to control bath temperature be 50～95 ℃.
6. the method for preparing vanadylic sulfate according to claim 5, is characterized in that, the described reaction times that Vanadium Pentoxide in FLAKES is dissolved in to the step of oxalic acid solution is 15～30min.
7. the method for preparing vanadylic sulfate according to claim 1, is characterized in that, described maturing temperature is 220～260 ℃, and roasting time is 30～60min.
8. the method for preparing vanadylic sulfate according to claim 1, is characterized in that, described vanadylic sulfate is Powdered.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979606A (en) * | 2014-05-29 | 2014-08-13 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing vanadyl sulfate |
| CN107557598A (en) * | 2017-05-25 | 2018-01-09 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| CN108878944A (en) * | 2018-03-08 | 2018-11-23 | 湖南三丰钒业有限公司 | A method of electrolyte of vanadium redox battery is prepared using waste vanadium catalyst |
| CN114436328A (en) * | 2022-03-14 | 2022-05-06 | 中国科学院过程工程研究所 | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution |
| CN114772642A (en) * | 2022-04-22 | 2022-07-22 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN114853064A (en) * | 2022-05-25 | 2022-08-05 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadyl sulfate solution with assistance of microbubbles |
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| JP2005060155A (en) * | 2003-08-11 | 2005-03-10 | Nippon Oil Corp | Method of producing tetravalent vanadyl sulfate aqueous solution |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979606A (en) * | 2014-05-29 | 2014-08-13 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing vanadyl sulfate |
| CN107557598A (en) * | 2017-05-25 | 2018-01-09 | 中国科学院过程工程研究所 | The method for preparing V electrolyte |
| 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 |
| CN108878944A (en) * | 2018-03-08 | 2018-11-23 | 湖南三丰钒业有限公司 | A method of electrolyte of vanadium redox battery is prepared using waste vanadium catalyst |
| CN114436328A (en) * | 2022-03-14 | 2022-05-06 | 中国科学院过程工程研究所 | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution |
| CN114772642A (en) * | 2022-04-22 | 2022-07-22 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN114772642B (en) * | 2022-04-22 | 2024-03-01 | 中国科学院过程工程研究所 | Preparation method of high-purity vanadyl sulfate solution |
| CN114853064A (en) * | 2022-05-25 | 2022-08-05 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadyl sulfate solution with assistance of microbubbles |
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