CN104692461A - Method for preparing high-purity powdered vanadium oxide - Google Patents
Method for preparing high-purity powdered vanadium oxide Download PDFInfo
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- CN104692461A CN104692461A CN201510082939.1A CN201510082939A CN104692461A CN 104692461 A CN104692461 A CN 104692461A CN 201510082939 A CN201510082939 A CN 201510082939A CN 104692461 A CN104692461 A CN 104692461A
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Abstract
The invention relates to a method for preparing high-purity powdered vanadium oxide and belongs to the technical field of chemical metallurgy of vanadium. The technical scheme of the invention is as follows: the method comprises the steps: adding an adsorbent, an acidity/basicity regulator and an impurity remover into a vanadium solution which serves as a raw material, mixing, stirring, and then, filtrating so as to obtain a purified vanadium solution; supplementing NH4<+> into the purified vanadium solution, adjusting the concentration of the NH4<+> in the purified vanadium solution, cooling to crystallize, and filtrating, so as to obtain ammonium metavanadate; enabling ammonium metavanadate to be subjected to 300-650 DEG C thermal decomposition and deamination, thereby obtaining powdered vanadium oxide, wherein the high-purity powdered vanadium oxide is suitable for producing a vanadium electrolyte. According to the method, a process of controlling the impurity content of a leachate at source is adopted, so that subsequent impurity removal processing steps are simplified, the consumption of chemicals is lowered, the production cost is low, the process is clean, and thus, industrial production is facilitated.
Description
Technical field
The invention belongs to vanadium field of chemical metallurgical technology, be specifically related to a kind of preparation method of high-purity vanadium oxide powder.
Background technology
The traditional method that Vanadium Pentoxide in FLAKES is produced is vanadium slag sodium roasting-ammonium salt precipitation method, and wherein the vanadium product of more than 65% comes from this method.The ammonium salt precipitator method have two kinds: a kind of is first the pH value of the solution containing pentavalent vanadium is adjusted to 8.5 ~ 9.5, then presses V in solution
2o
5ammonium salt Precipitation ammonium meta-vanadate is added with mass ratio 1:1.3 ~ 1.5 of ammonium salt; Another kind adopts substep to reconcile pH value to 1.5 ~ 2.5 of solution, adds ammonium salt Precipitation ammonium poly-vanadate, after the ammonium meta-vanadate obtained or ammonium poly-vanadate are obtained Vanadium Pentoxide in FLAKES through calcining.The impurity carried secretly due to precipitation process does not have suitable method to be removed in follow-up operation, so the Vanadium Pentoxide in FLAKES foreign matter content adopting above technique to obtain is higher, the grade of Vanadium Pentoxide in FLAKES only has about 98%, containing impurity elements such as Fe, Al, K, Na, Ca, Mg, Si, P, S and As, be difficult to meet the requirement of multiple field to purity of vanadium pentoxide.
And the development that the widespread use of special efficacy vanadium catalyst in recent years and vanadium cell are studied, more and more higher to the requirement of high purity V and its compounds.At present, the production purification process of domestic and international high purity vanadic anhydride mainly comprises solvent extration, ion exchange method and the scavenging agent method of purification based on precipitation, coprecipitation method.Wherein: vanadium effectively can be extracted into organic phase by solvent extration, eventually pass reextraction and obtain containing vanadium solution.Original low vanadium solution can be made to obtain enrichment method simultaneously.The vanadium extraction agent industrially applied at present mainly comprises propionic acid penta fat, two-2-ethylhexyl phosphoric acid, tbp, trialkylamine, chlorination trialkyl methyl amine etc.
Ion-exchange is mainly different from the ability that vanadic acid radical ion adsorbs (chelating) on ion exchange resin by impurity element, thus reaches the object of separating-purifying.In the purification process of vanadium, because vanadium exists with vanadium acid anion state, and most of foreign ion exists with cationic state, and anionite-exchange resin therefore can be used to carry out the purification of vanadium.The resin anion(R.A) being usually used in vanadium purification comprises Amberlite, IRA-400, IRA-401, IRA-402, IRA-410, IRA-420, DOWEX-1, DOWEX-2 etc.
The scavenging agent method of purification mainly selects can to form precipitation with impurity element, the ion of co-precipitation carries out removal of impurities, and conventional scavenging agent comprises soluble calcium salt, solubility magnesium salts, solubility villaumite, sodium hydroxide or sodium carbonate etc.Chinese invention patent application publication number CN 102923776A discloses a kind of method that high purity vanadic anhydride produced by ammonium meta-vanadate, be specially: the deionized water rough ammonium meta-vanadate being dissolved in 85-95 DEG C, the pH value of sodium hydrate regulator solution is adjusted to 8-10, add calcium chloride removal of impurities, further the pH value of filtrate is adjusted to 10-12 removal of impurities again, in filtrate, pressurization passes into ammonia, release; Ultrasonic atomization, condensation-crystallization met by ammonium meta-vanadate, and after the washing of scraping crystal water, at 500-550 DEG C, calcining obtains the Vanadium Pentoxide in FLAKES that purity is 99.95%.
These three kinds of techniques are prepared by each vanadium the purification that enterprise is widely used in vanadium solution at present, but come with some shortcomings simultaneously, wherein: organic reagent, have certain pollution to environment; Need to use the exchange resin having special efficacy functional group, cost for purification is higher; The precipitator method, need to add the isoionic scavenging agent of a large amount of calcic, magnesium, aluminium or sodium, and production cost is higher and easily cause these element single indexs in product to exceed standard.
Summary of the invention
The invention provides the preparation method of a kind of Gaochun vanadium oxide powder, the technical problem of solution is the purification schemes simplifying high purity vanadium, reduces the use of additives, reduces cost for purification, improves vanadium products production efficiency, realizes the cleaner production of high purity vanadium.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: with vanadium liquid for raw material, add sorbent material in vanadium liquid, acid-base modifier and cleaner, after mix and blend, filters, is purified vanadium liquid;
2) precipitation: supplement NH to described purification vanadium liquid
4 +, regulate NH in purification vanadium liquid
4 +concentration, crystallisation by cooling, filters and obtains ammonium meta-vanadate;
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 300-650 DEG C of thermal degradation deamination.
Step 1) acid-base modifier of the present invention is Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, regulation and control vanadium liquid pH value is 7-14.
In step 1) of the present invention, in vanadium liquid, v element content is 10-50g/L.
Step 2 of the present invention) middle benefit NH
4 +method is: be blown into liquefied ammonia gas or add volatile salt, bicarbonate of ammonia in purification vanadium liquid, NH in adjustment purification vanadium liquid
4 +concentration is 1-150g/L.
In step 1) of the present invention, sorbent material is gac, Al
2o
3, Al (OH)
3in any one or a few, addition is the 0.1-20% of vanadium liquid weight.
In step 1) of the present invention, cleaner is CaO, Ca (OH)
2, Ca (CO
3)
2in any one or a few, addition be the 1-10 of P weight in vanadium liquid doubly.
Step 2 of the present invention) middle Crystallisation pH is 7 ~ 11, temperature is 0-30 DEG C, rearing crystal time is 0.5-2h, crystallisation by cooling precipitation ammonium meta-vanadate.
Step 2 of the present invention) in ammonium meta-vanadate purity higher than 99.8wt%.
In step 3) of the present invention, vanadium oxide powder purity is 99.9wt%, is suitable for producing V electrolyte.
In step 1) of the present invention, vanadium liquid is the vanadium liquid of vanadium slag saltless roasting ammonium leaching and vanadium extraction flow process.
The beneficial effect adopting technique scheme to produce is: the vanadium oxide powder that gained ammonium meta-vanadate obtains after deamination is suitable for producing V electrolyte; The present invention adopts the technique of Sources controlling leach liquor foreign matter content, and simplify follow-up impurity removal process step, reduce reagent consumption, production cost is low, and process cleans is conducive to industrial production.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1:
1. a preparation method for high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: be add sorbent material, cleaner, acid-base modifier Na in the vanadium liquid of 30g/L to v element content
2cO
3regulation and control vanadium liquid pH value is 11, after mix and blend, filters and is purified vanadium liquid;
Sorbent material is gac, Al (OH)
3deng mass mixing thing, addition is 8% of vanadium liquid weight; Cleaner is CaO, and addition is 3 times of P weight in vanadium liquid; Vanadium liquid is the vanadium liquid of vanadium slag saltless roasting ammonium leaching and vanadium extraction flow process.
2) precipitation: be blown into liquefied ammonia gas to purification vanadium liquid, regulate NH
4 +concentration is 10g/L, pH value be 9, temperature be 30 DEG C of conditions under crystallisation by cooling, rearing crystal time is 1.5h, filter obtain ammonium meta-vanadate, purity is 99.90%.
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 650 DEG C of thermal degradation deaminations, purity is 99.91%, and this product is applicable to produce V electrolyte.
Embodiment 2:
A preparation method for high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: be add sorbent material, cleaner, acid-base modifier (NH in the vanadium liquid of 45g/L to v element content
4)
2cO
3regulation and control vanadium liquid pH value is 14, after mix and blend, filters and is purified vanadium liquid;
Sorbent material is gac and Al
2o
3mass ratio is the mixture of 1:2, and addition is 16% of vanadium liquid weight; Cleaner is CaO, and addition is 2 times of P weight in vanadium liquid; Vanadium liquid is the vanadium liquid of vanadium slag saltless roasting ammonium leaching and vanadium extraction flow process.
2) precipitation: add volatile salt to purification vanadium liquid, regulate NH
4 +concentration is 50g/L, pH value be 10, temperature be 20 DEG C of conditions under crystallisation by cooling, rearing crystal time is 2h, filter obtain ammonium meta-vanadate, ammonium meta-vanadate purity is 99.83wt%.
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 300 DEG C of thermal degradation deaminations, purity is 99.81%, and this product is applicable to produce V electrolyte.
Embodiment 3:
1. a preparation method for high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: be add sorbent material, cleaner, acid-base modifier (NH in the vanadium liquid of 10g/L to v element content
4)
2cO
3regulation and control vanadium liquid pH value is 7, after mix and blend, filters and is purified vanadium liquid;
Sorbent material is Al (OH)
3, addition is 0.1% of vanadium liquid weight; Cleaner is Ca (OH)
2, addition is 1 times of P weight in vanadium liquid.
2) precipitation: add bicarbonate of ammonia to purification vanadium liquid, regulate NH
4 +concentration is 1g/L, pH value be 7, temperature be 0 DEG C of condition under crystallisation by cooling, rearing crystal time is 2h, filter obtain ammonium meta-vanadate, purity is 99.90 wt%.
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 450 DEG C of thermal degradation deaminations, purity is 99.90%, and this product is applicable to produce V electrolyte.
Embodiment 4:
A preparation method for high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: be add sorbent material, cleaner, acid-base modifier NH in the vanadium liquid of 50g/L to v element content
4hCO
3regulation and control vanadium liquid pH value is 10, after mix and blend, filters and is purified vanadium liquid;
Sorbent material is gac, Al
2o
3, Al (OH)
3deng mass mixing thing, addition is 20% of vanadium liquid weight; Cleaner is CaCO
3, addition is 10 times of P weight in vanadium liquid.
2) precipitation: be blown into liquefied ammonia gas in purification vanadium liquid, regulate NH
4 +concentration is 150g/L, pH value be 11, temperature be 4 DEG C of conditions under crystallisation by cooling, rearing crystal time is 0.5h, filter obtain ammonium meta-vanadate, purity is 99.86wt%.
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 500 DEG C of thermal degradation deaminations, purity is 99.89%, and this product is applicable to produce high purity vanadium aluminium alloy.
Embodiment 5:
A preparation method for high-purity vanadium oxide powder, described processing step is as follows:
1) vanadium liquid purification: be add sorbent material, cleaner, acid-base modifier NH in the vanadium liquid of 28g/L to v element content
4hCO
3regulation and control vanadium liquid pH value is 9, after mix and blend, filters and is purified vanadium liquid;
Sorbent material is gac, Al
2o
3, addition is 10% of vanadium liquid weight; Cleaner is CaO and CaCO
3mass ratio is the mixture of 2:1, and addition is 7 times of P weight in vanadium liquid; Vanadium liquid is the vanadium liquid of vanadium slag saltless roasting ammonium leaching and vanadium extraction flow process.
2) precipitation: add volatile salt in purification vanadium liquid, regulate NH
4 +concentration is 78g/L, pH value be 8, temperature be 8 DEG C of conditions under crystallisation by cooling, rearing crystal time is 1h, filter obtain ammonium meta-vanadate, purity is 99.85wt%.
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 600 DEG C of thermal degradation deaminations, purity is 99.91%, and this product is applicable to produce vanadium catalyst.
Claims (10)
1. a preparation method for high-purity vanadium oxide powder, is characterized in that, described processing step is as follows:
1) vanadium liquid purification: with vanadium liquid for raw material, add sorbent material in vanadium liquid, acid-base modifier and cleaner, after mix and blend, filters, is purified vanadium liquid;
2) precipitation: supplement NH to described purification vanadium liquid
4 +, regulate NH in purification vanadium liquid
4 +concentration, crystallisation by cooling, filters and obtains ammonium meta-vanadate;
3) roasting: the vanadium oxide powder that described ammonium meta-vanadate obtains after 300-650 DEG C of thermal degradation deamination.
2. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1, is characterized in that: in described step 1), acid-base modifier is Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, regulation and control vanadium liquid pH value is 7-14.
3. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1, is characterized in that, in described step 1), in vanadium liquid, v element content is 10-50g/L.
4. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1, is characterized in that: described step 2) middle benefit NH
4 +method is: be blown into liquefied ammonia gas or add volatile salt, bicarbonate of ammonia in purification vanadium liquid, NH in adjustment purification vanadium liquid
4 +concentration is 1-150g/L.
5. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, in described step 1), sorbent material is gac, Al
2o
3, Al (OH)
3in any one or a few, addition is the 0.1-20% of vanadium liquid weight.
6. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, in described step 1), cleaner is CaO, Ca (OH)
2, Ca (CO
3)
2in any one or a few, addition be the 1-10 of P weight in vanadium liquid doubly.
7. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, described step 2) middle Crystallisation pH is 7 ~ 11, temperature is 0-30 DEG C, rearing crystal time is 0.5-2h, crystallisation by cooling precipitation ammonium meta-vanadate.
8. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, described step 2) in ammonium meta-vanadate purity higher than 99.8wt%.
9. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, in described step 3), vanadium oxide powder purity is 99.9wt%, is suitable for producing V electrolyte.
10. the preparation method of a kind of high-purity vanadium oxide powder according to claim 1-4 any one, is characterized in that, in described step 1), vanadium liquid is the vanadium liquid of vanadium slag saltless roasting ammonium leaching and vanadium extraction flow process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106241873A (en) * | 2016-08-26 | 2016-12-21 | 陕西华源矿业有限责任公司 | The preparation method of high-purity vanadium pentoxide |
| WO2017092217A1 (en) * | 2015-12-02 | 2017-06-08 | 四川行之智汇知识产权运营有限公司 | Method for producing high-purity vanadium pentoxide by room temperature extraction |
| CN108517424A (en) * | 2018-04-08 | 2018-09-11 | 河钢股份有限公司承德分公司 | A method of being ultrasonically treated precipitation |
| CN109081374A (en) * | 2018-10-19 | 2018-12-25 | 河钢股份有限公司承德分公司 | A method of preparing the spherical ammonium poly-vanadate of big granularity |
| CN109399712A (en) * | 2018-12-11 | 2019-03-01 | 联和能源投资控股有限公司 | A method of with hydrogen peroxide clean manufacturing high purity vanadic anhydride |
| CN113732297A (en) * | 2021-09-04 | 2021-12-03 | 湖南众鑫新材料科技股份有限公司 | High-purity vanadium purification process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531054A (en) * | 2010-12-27 | 2012-07-04 | 邓时胜 | Purification method of ammonium metavanadate and preparation method of high-purity vanadium pentoxide |
| CN102923776A (en) * | 2012-12-03 | 2013-02-13 | 张春雨 | Method for producing high-purity vanadium pentoxide |
-
2015
- 2015-02-16 CN CN201510082939.1A patent/CN104692461A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531054A (en) * | 2010-12-27 | 2012-07-04 | 邓时胜 | Purification method of ammonium metavanadate and preparation method of high-purity vanadium pentoxide |
| CN102923776A (en) * | 2012-12-03 | 2013-02-13 | 张春雨 | Method for producing high-purity vanadium pentoxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017092217A1 (en) * | 2015-12-02 | 2017-06-08 | 四川行之智汇知识产权运营有限公司 | Method for producing high-purity vanadium pentoxide by room temperature extraction |
| CN106241873A (en) * | 2016-08-26 | 2016-12-21 | 陕西华源矿业有限责任公司 | The preparation method of high-purity vanadium pentoxide |
| CN108517424A (en) * | 2018-04-08 | 2018-09-11 | 河钢股份有限公司承德分公司 | A method of being ultrasonically treated precipitation |
| CN109081374A (en) * | 2018-10-19 | 2018-12-25 | 河钢股份有限公司承德分公司 | A method of preparing the spherical ammonium poly-vanadate of big granularity |
| CN109399712A (en) * | 2018-12-11 | 2019-03-01 | 联和能源投资控股有限公司 | A method of with hydrogen peroxide clean manufacturing high purity vanadic anhydride |
| CN113732297A (en) * | 2021-09-04 | 2021-12-03 | 湖南众鑫新材料科技股份有限公司 | High-purity vanadium purification process |
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