CN104628033A - Method for preparing metavanadate - Google Patents
Method for preparing metavanadate Download PDFInfo
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- CN104628033A CN104628033A CN201510039198.9A CN201510039198A CN104628033A CN 104628033 A CN104628033 A CN 104628033A CN 201510039198 A CN201510039198 A CN 201510039198A CN 104628033 A CN104628033 A CN 104628033A
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- metavanadate
- calcium
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- sodium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- 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 relates to a method for preparing metavanadate. The method comprises the following steps: adding a calcium precipitator into a sodium treatment vanadium recovery leaching solution to react for 30-40 minutes, performing liquid-solid separation, washing, and filtering, thereby obtaining calcium vanadate solids; adding the calcium vanadate solids and water into a reactor, stirring, heating, adding bicarbonate, adding according to the molar ratio of metal cations to V of (0.8-1):1 in bicarbonate, introducing carbon dioxide gas, and heating to the temperature of 80-100 DEG C to react for 1-6 hours, thereby obtaining slurry containing metavanadate and calcium carbonate based on the moment when the pH value is 7.5-8.5 as the reaction endpoint; performing liquid-solid separation on the slurry, thereby obtaining the calcium carbonate solids and sodium metavanadate solution; and crystallizing the sodium metavanadate solution, and separating to obtain sodium metavanadate and crystallized solution, drying, thereby obtaining the sodium metavanadate solids. According to the method, vanadium liquid in the vanadium chemical production process can serve as a raw material, the metavanadate is prepared, the pollution problem of ammonia-nitrogen wastewater in the traditional ammonium precipitation process is solved, the complicated process is reduced, and the cost is reduced.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method of metavanadate.
Background technology
Sodium metavanadate, potassium metavanadate product respectively have two kinds of specifications, and its chemical constitution is as shown in table 1, table 2.Sodium metavanadate is widely used in chemical field, can be used as siccative, catalyzer, mordant etc., also can be used for medical image, plant inoculating and inhibitor etc.; Potassium metavanadate is mainly used as chemical reagent, catalyzer, siccative, mordant etc.
At present, sodium metavanadate is all produce based on the finished product in vanadium slag sodium roasting production vanadium process or intermediates.One method is that adjust ph, evaporation, crystallization obtain sodium metavanadate solid by after the removal of impurities of vanadium extraction leach liquor.Another kind method is that Vanadium Pentoxide in FLAKES or ammonium vanadate and sodium hydroxide are obtained sodium metavanadate.
Wherein method one is by after the removal of impurities of vanadium extraction leach liquor, through evaporating, concentrating and crystallizing after adjust ph, thus obtains sodium metavanadate solid.The method technique is simple, easy to operate, but vanadium extraction leach liquor complicated component, Impurity removal is incomplete, and cause product purity not high, therefore the method is difficult to be used widely, in the process of adjust ph in addition, introduce the impurity such as sulfate radical, cause crystal solution not reuse, produce a large amount of waste water.
Method two dissolves powdery Vanadium Pentoxide in FLAKES with sodium hydroxide or potassium hydroxide solution under the condition of heating, fully obtains vanadic acid sodium, potassium metavanadate solution after reaction, then obtain sodium metavanadate by crystallization.This method is simple to operate, and the product purity obtained is higher, does not produce and pollutes waste gas (ammonia), is to use method comparatively widely at present.But the raw materials for production Vanadium Pentoxide in FLAKES of the method obtains ammonium vanadate to vanadium liquid through ammonium is heavy, and calcining obtains Vanadium Pentoxide in FLAKES, and this technique produces the environmental problem of a large amount of ammonia nitrogen waste waters; Higher to the specification of quality of Vanadium Pentoxide in FLAKES in addition, operation is loaded down with trivial details, and therefore production cost is high.
Another method be as in the patent application of publication number for CN101723455A mention, utilize vanadium extraction leach liquor first to leach many vanadic acid sodiums, then produce sodium metavanadate by sodium hydroxide dissolution method.The shortcoming of the method needs pH value to be adjusted to 1.1 ~ 1.6 in the process of the many vanadic acid sodiums of precipitation, and the consumption of acid is comparatively large, and precipitation process control difficulties is large and vanadium yield is low.
Equally, also there are the problems referred to above in potassium metavanadate process of producing product.
Table 1 sodium metavanadate product chemical constitution
Table 2 potassium metavanadate product chemical constitution
Summary of the invention
The object of the present invention is to provide a kind of preparation method of metavanadate, the method for raw material prepares sodium metavanadate, potassium metavanadate, solves the sodium metavanadate in this area with the leach liquor vanadium liquid of vanadium chemical process, potassium metavanadate prepares Problems existing.
In order to reach above object, the preparation method of a kind of metavanadate provided by the invention comprises the following steps: 1) sodium vanadium extraction leach liquor is placed in reactor, be heated to 80 ~ 100 DEG C, in sodium vanadium extraction leach liquor, calcium deposit agent is added according to the mol ratio of Ca:V=1.5:1 ~ 2:1, react after 30 ~ 40 minutes, obtain calcium vanadate solid through solid-liquor separation, washing, filtration;
2) the calcium vanadate solid of step 1) gained and a certain amount of water are added in the lump hold in reactor, and open stirring and heating, add supercarbonate, add according to the mol ratio of metallic cation in supercarbonate: V=0.8 ~ 1:1, and pass into carbon dioxide, be heated to 80 ~ 100 DEG C, reaction 1 ~ 6h, be 7.5 ~ 8.5 for reaction end with pH, obtain the slurry containing metavanadate and calcium carbonate;
3) step 2) described slurry through solid-liquor separation, obtain calcium carbonate solid and metavanadate solution; By obtained metavanadate solution through crystallization, be separated and obtain liquid after metavanadate and crystallization, and drying below 40 DEG C, thus obtain metavanadate solid;
4) calcium carbonate solid step 3) obtained carries out washing, filtering, and obtains washings and calcium carbonate.
Step 2 of the present invention) in the supercarbonate that adds be sodium bicarbonate or saleratus.
In step 4) of the present invention, metavanadate solid is sodium metavanadate or potassium metavanadate.
Calcium deposit agent in step 1) of the present invention is calcium oxide or calcium hydroxide, and the calcium vanadate solid obtained is the mixture of calcium vanadate and calcium hydroxide.
Step 2 of the present invention) air flow of carbonic acid gas is unit quality calcium vanadate 0.1 ~ 1L/ (minKg).
Metavanadate strength of solution in step 3) of the present invention is 80 ~ 200g/L.
Crystallization condition in step 3) of the present invention is under normal temperature condition, places crystallization or stirred crystallization.
Water lotion after step 3) crystallization of the present invention in liquid and described step 4) returns step 2) substitute water and use.
Calcium carbonate in step 4) of the present invention uses as calcium deposit agent after roasting.
The carbonic acid gas generated in calcium carbonate roasting process of the present invention replaces step 2 for part) in required carbonic acid gas.
Beneficial effect of the present invention is: the present invention adopts vanadium leachate to be the method that metavanadate (i.e. sodium metavanadate or potassium metavanadate) prepared by raw material, the method not only fundamentally avoids the environmental problem such as waste water, waste gas that traditional technology is brought, also can reduce preparation section, there is economic benefit environmental benefit significantly.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
A kind of preparation method of metavanadate: the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience is placed in reactor, be heated to 80 DEG C, in sodium vanadium extraction leach liquor, calcium oxide is added according to the mol ratio of Ca:V=1.5:1, react after 30 minutes, obtain containing V=20%, Ca=40% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and open stirring and heating, sodium bicarbonate 92g is added according to the mol ratio of Na:V=1:1, and pass into carbon dioxide, air flow is 0.8L/ (minKg), be heated to 80 DEG C, record after reaction 6h, pH is 8.3; 3) solid-liquor separation obtains calcium carbonate solid and sodium metavanadate solution, and strength of solution is 200g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 8h, be separated and obtain sodium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 98.6% sodium metavanadate.
Embodiment 2
A kind of preparation method of metavanadate: in the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience and reactor, be heated to 100 DEG C, in sodium vanadium extraction leach liquor, calcium hydroxide slurry is added according to the mol ratio of Ca:V=2:1, react after 40 minutes, obtain containing V=19%, Ca=43% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and open stirring and heating, sodium bicarbonate 88g is added according to the mol ratio of Na:V=0.8:1, and pass into carbon dioxide, air flow is 0.1L/ (minKg), be heated to 100 DEG C, record after reaction 2h, pH is 8.2; 3) solid-liquor separation obtains calcium carbonate solid and sodium metavanadate solution, and strength of solution is 80g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 8h, be separated and obtain sodium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 98.3% sodium metavanadate.
Embodiment 3
A kind of preparation method of metavanadate: in the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience and reactor, be heated to 93 DEG C, in sodium vanadium extraction leach liquor, calcium hydroxide slurry is added according to the mol ratio of Ca:V=1.8:1, react after 35 minutes, obtain containing V=19%, Ca=43% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and opens stirring and heating, adds sodium bicarbonate according to the mol ratio of Na:V=0.9:1
99g, and pass into carbon dioxide, air flow is 0.5L/ (minKg), is heated to 88 DEG C, and record after reaction 1h, pH is 8.5; 3) solid-liquor separation obtains calcium carbonate solid and sodium metavanadate solution, and strength of solution is 120g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 8h, be separated and obtain sodium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 98.1% sodium metavanadate.
Embodiment 4
A kind of preparation method of metavanadate: in the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience and reactor, be heated to 80 DEG C, in sodium vanadium extraction leach liquor, calcium oxide is added according to the mol ratio of Ca:V=1.5:1, react after 30 minutes, obtain containing V=20%, Ca=40% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and open stirring and heating, saleratus 110g is added according to the mol ratio of K:V=1:1, pass into carbon dioxide, air flow is 0.8L/ (minKg), be heated to 80 DEG C, record after reaction 2h, pH is 7.8.3) solid-liquor separation obtains calcium carbonate solid and potassium metavanadate solution, and strength of solution is 180g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 10h, be separated and obtain potassium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 99.1% potassium metavanadate.
Embodiment 5
A kind of preparation method of metavanadate: in the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience and reactor, be heated to 86 DEG C, in sodium vanadium extraction leach liquor, calcium hydroxide slurry is added according to the mol ratio of Ca:V=2:1, react after 40 minutes, obtain containing V=19%, Ca=43% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and open stirring and heating, saleratus 105g is added according to the mol ratio of K:V=0.8:1, and pass into carbon dioxide, air flow is 1L/ (minKg), be heated to 100 DEG C, record after reaction 1h, pH is 7.9; 3) solid-liquor separation obtains calcium carbonate solid and potassium metavanadate solution, and strength of solution is 80g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 8h, be separated and obtain sodium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 98.9% potassium metavanadate.
Embodiment 6
A kind of preparation method of metavanadate: in the sodium vanadium extraction leach liquor after removal of impurities of 1) learning from else's experience and reactor, be heated to 100 DEG C, in sodium vanadium extraction leach liquor, calcium hydroxide slurry is added according to the mol ratio of Ca:V=1.6:1, react after 40 minutes, obtain containing V=19%, Ca=43% calcium vanadate solid after solid-liquor separation, washing, filtration, oven dry; 2) water getting solid 300g and the 500mL of calcium vanadate of step 1) gained adds in beaker in the lump, and open stirring and heating, saleratus 125g is added according to the mol ratio of K:V=0.95:1, and pass into carbon dioxide, air flow is 0.8L/ (minKg), be heated to 96 DEG C, record after reaction 6h, pH is 7.5; 3) solid-liquor separation obtains calcium carbonate solid and potassium metavanadate solution, and strength of solution is 150g/L; Placed with container, open stirring and carry out spontaneous nucleation, after crystallization time 8h, be separated and obtain sodium metavanadate crystal, and 40 DEG C of dryings, obtaining purity is 99.1% potassium metavanadate.
Above by embodiment to invention has been detailed description; but described content is only preferred embodiment of the present invention; utilize technical solutions according to the invention; or those skilled in the art is under the inspiration of technical solution of the present invention; design similar technical scheme; and reach above-mentioned technique effect, be all fall into protection scope of the present invention.
Claims (10)
1. a preparation method for metavanadate, is characterized in that, the method comprises the following steps:
1) sodium vanadium extraction leach liquor is placed in reactor, be heated to 80 ~ 100 DEG C, in sodium vanadium extraction leach liquor, add calcium deposit agent according to the mol ratio of Ca:V=1.5:1 ~ 2:1, react after 30 ~ 40 minutes, obtain calcium vanadate solid through solid-liquor separation, washing, filtration;
2) the calcium vanadate solid of step 1) gained and a certain amount of water are added in the lump hold in reactor, and open stirring and heating, add supercarbonate, add according to the mol ratio of metallic cation in supercarbonate: V=0.8 ~ 1:1, and pass into carbon dioxide, be heated to 80 ~ 100 DEG C, reaction 1 ~ 6h, be 7.5 ~ 8.5 for reaction end with pH, obtain the slurry containing metavanadate and calcium carbonate;
3) step 2) described slurry through solid-liquor separation, obtain calcium carbonate solid and metavanadate solution; By obtained metavanadate solution through crystallization, be separated and obtain liquid after metavanadate and crystallization, and drying below 40 DEG C, thus obtain metavanadate solid;
4) calcium carbonate solid step 3) obtained carries out washing, filtering, and obtains washings and calcium carbonate.
2. the preparation method of a kind of metavanadate according to claim 1, is characterized in that, described step 2) in the supercarbonate that adds be sodium bicarbonate or saleratus.
3. the preparation method of a kind of metavanadate according to claim 2, is characterized in that, in described step 4), metavanadate solid is sodium metavanadate or potassium metavanadate.
4. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, the calcium deposit agent in described step 1) is calcium oxide or calcium hydroxide, and the calcium vanadate solid obtained is the mixture of calcium vanadate and calcium hydroxide.
5. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, described step 2) air flow of carbonic acid gas is unit quality calcium vanadate 0.1 ~ 1L/ (minKg).
6. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, the metavanadate strength of solution in described step 3) is 80 ~ 200g/L.
7. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, the crystallization condition in described step 3) is under normal temperature condition, places crystallization or stirred crystallization.
8. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, the water lotion after described step 3) crystallization in liquid and described step 4) returns step 2) substitute water and use.
9. the preparation method of a kind of metavanadate according to claim 1-3 any one, is characterized in that, the calcium carbonate in described step 4) uses as calcium deposit agent after roasting.
10. the preparation method of a kind of metavanadate according to claim 9, is characterized in that, the carbonic acid gas generated in described calcium carbonate roasting process replaces step 2 for part) in required carbonic acid gas.
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| CN201510039198.9A CN104628033A (en) | 2015-01-27 | 2015-01-27 | Method for preparing metavanadate |
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| CN201510039198.9A CN104628033A (en) | 2015-01-27 | 2015-01-27 | Method for preparing metavanadate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107937737A (en) * | 2017-11-24 | 2018-04-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for reducing chromium content in high chromium calcium vanadate |
| CN108588737A (en) * | 2018-05-09 | 2018-09-28 | 湖南钒谷新能源技术有限公司 | A method of processing vanadium-containing waste liquid prepares sodium metavanadate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723455A (en) * | 2009-12-29 | 2010-06-09 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing sodium metavanadate |
| CN102531055A (en) * | 2011-12-14 | 2012-07-04 | 攀钢集团有限公司 | Method for preparing sodium metavanadate/potassium metavanadate |
-
2015
- 2015-01-27 CN CN201510039198.9A patent/CN104628033A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723455A (en) * | 2009-12-29 | 2010-06-09 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing sodium metavanadate |
| CN102531055A (en) * | 2011-12-14 | 2012-07-04 | 攀钢集团有限公司 | Method for preparing sodium metavanadate/potassium metavanadate |
Non-Patent Citations (1)
| Title |
|---|
| 申小清等: "从含钒酸浸液中回收钒的工艺研究", 《河南化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107937737A (en) * | 2017-11-24 | 2018-04-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for reducing chromium content in high chromium calcium vanadate |
| CN108588737A (en) * | 2018-05-09 | 2018-09-28 | 湖南钒谷新能源技术有限公司 | A method of processing vanadium-containing waste liquid prepares sodium metavanadate |
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Application publication date: 20150520 |