CN102430266B - Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide - Google Patents
Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide Download PDFInfo
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- CN102430266B CN102430266B CN201010501816.4A CN201010501816A CN102430266B CN 102430266 B CN102430266 B CN 102430266B CN 201010501816 A CN201010501816 A CN 201010501816A CN 102430266 B CN102430266 B CN 102430266B
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Abstract
The invention provides a method for purifying liquid with vanadium, comprising the following steps: contacting the liquid with vanadium with acid cation exchange resin for ion exchange; and separating the liquid with vanadium after being contacted from the acid cation exchange resin, wherein the liquid with vanadium comprises metal cations and acid group anions of the vanadium. The method can be easily operated, has a few steps and low cost, can be used for processing the high-concentration liquid with vanadium and reducing the combustion of precipitator, so the supernatant liquid of the precipitated vanadium can be directly recycled, the yield of the vanadium is improved, and the grade of the vanadium oxide is improved.
Description
Technical field
The present invention relates to a kind of containing the purification process of vanadium solution and the preparation method of ammonium metavanadate and vanadium oxide.
Background technology
Vanadium is dystectic rare metal, has a lot of good performances, has been widely used in industries such as metallurgy, chemical industry.Vanadium for steel and iron industry, adds 0.1%～0.5% vanadium and carbon Formed compound in steel, refinement matrix grain, thus improve the performance of steel; The high oxide of vanadium is the important catalyst in chemical industry and petroleum industry; In addition,, in industry such as electronics, glass, printing, film, photograph and potteries, the compound of vanadium is also used widely.And along with the high speed development of China's modernization construction, the demand of vanadium and its compound is increasing, the scope of application is more and more wider, and its quality requirement is also more and more higher.
In the prior art of precipitation: within (1) 2003 year, Lee is marked on greatly " research of acid ammonium salt precipitation condition experiment ", " process engineering journal ", 2003, NO.3 (1), in P.53～56 documents, the precipitation method of proposition is taking the solution containing vanadium 30g/L left and right as raw material, after adding ammonium sulfate, use sulphur acid for adjusting pH to 2.2 left and right, add ammonium coefficient 2.2, in boiling water bath (95 DEG C), precipitation obtains containing Na 0.70%～1.08%, the APV of S 0.78%～1.20%.The shortcoming of this method is: impurity K, Na in precipitated product, S content are high, and vanadium product grade is low.
The precipitation method that the people such as (2) 2007 years Peng Yi propose in CN101157478A be taking traditional sodium roasting-water logging explained hereafter containing vanadium solution as raw material, first make vanadium be combined with the calcium compound adding and generate vanadic acid calcium, then react with vanadic acid calcium with carbonic hydroammonium, make vanadium proceed to solution, and calcium generates the more calcium carbonate of indissoluble, solution after separation generates ammonium poly-vanadate under suitable pH and heating condition, contains S 0.04～0.43% in products obtained therefrom.The shortcoming of this method is: production process is longer, and in product, S content is high.
Within (3) 2007 years, the Jia Shao precipitation method that just people such as grade proposes in CN101182036A is to adopt aluminum sulfate to purify vanadium solution, by hydrochloric acid adjusting vanadium solution pH value, filtrate adds ammonium chloride reaction 3～4 days, and after centrifugal dehydration, calcination 6～8 hours, obtains vanadic anhydride product.The shortcoming of this method is: the production cycle is long, and efficiency is low; In waste water, chlorine ion concentration is high, and intractability is large.
The precipitation method that the people such as (4) 1992 years Deng Qingyun propose in CN1065494A is with passing through large aperture weak-base anion-exchange resin bed containing vanadium solution and alkaline leacheate compartment of terrain, collect the solution up to 60～100g/L containing vanadium concentration, then connect vanadium oxide production technology.
The precipitation method that the people such as (5) 1998 years Ouyang Changlun propose in CN1235201A be the macroporous weakly basic anion exchange resin that filling with basket directly immerse leaching containing adsorbing vanadium in navajoite slurry, then use alkali lye desorb vanadium, resin, with returning to absorption after dilution heat of sulfuric acid regeneration, connects existing technique containing vanadium stripping liquid again and extracts vanadic anhydride.
The precipitation method that (6) 2006 years big vast sound proposes in CN101003855A is that roasting grog is less than to 0.1mm through wet grinding to fineness, keep pulp density 25～40%, ore pulp enters water logging tank diameter, to adding in tank diameter ore deposit to weigh 7～15% anionic resin, the vanadium ion in ore pulp is adsorbed, adsorb the alkali lye desorb of saturated resin; Stripping liquid is connect respectively to ammonium salt precipitation again.
The shortcoming of above-mentioned (4), (5), (6) method is: when a. adopts anion exchange resin to carry out enrichment to vanadium, also other impurity anion is carried out to enrichment, when precipitation, impurity also enters vanadium product together, vanadium product grade is low, generally not higher than 98.5%; B. vanadium solution concentration can not be too high, generally can not be higher than 30g/L, and concentration is higher, and impurity content is higher.
In addition, the common shortcoming of above all methods is: carry out precipitation with excessive ammonium salt, ammonium salt addition is large, and cost is high, and in waste water, ammonia content is high, and intractability is large; Waste water can not direct reuse, has reduced the yield of vanadium.
Therefore, urgently expect a kind ofly can process high concentration containing vanadium solution and can obtain the method for high-grade vanadium product.
Summary of the invention
The object of the invention is in order to overcome the problem that the gained vanadium product grade that the existing purification process containing vanadium solution exists is low, vanadium solution concentration can not be too high, a kind of high-grade vanadium product and can the purification process of purifying high vanadium concentrations solution and the preparation method of ammonium metavanadate and vanadium oxide of can obtaining is provided.
In known existing technology, all adopt anion exchange resin and exchange containing vanadium solution, vanadium ion is adsorbed on anion exchange resin, then by eluent, vanadium ion is eluted to reach the object of purifying.But, when adopting anion exchange resin to carry out enrichment to vanadium, also other impurity anion is carried out to enrichment, when precipitation, impurity also enters vanadium product together, and vanadium product grade is low, and vanadium solution concentration can not be too high simultaneously, and concentration is higher, and impurity content is higher.Simultaneously, due to the complicated component in vanadium solution that contains of sodium roasting-water logging explained hereafter, use existing precipitation technology to prepare high-grade vanadium oxide, program complexity, step is long, and, because adding ammonium salt, need remove the metal cation of being combined with vanadium in substitutional solution, and vanadium is combined with ammonia and generates precipitation, the associativity of monovalent cation and vanadium is best, monovalent cation is more, and the ammonium salt adding is just more, and therefore ammonium salt addition is large.
The inventor finds unexpectedly, by contacting with acid cation exchange resin containing vanadium solution of sodium roasting-water logging explained hereafter, carry out ion-exchange, hydrogen ion in acid cation exchange resin enters vanadium solution, metal cation in vanadium solution is held back by acid cation exchange resin, thereby the separating of isopolyacid radical ion of realizing metal cation and vanadium, recycling precipitating reagent makes vanadium precipitation, will after the high-temperature roasting of vanadium sediment, can obtain high-grade vanadium oxide.The simple easy operating of the method, step is few, and cost is low, can process the vanadium solution that contains of high concentration, can also reduce the consumption of precipitating reagent simultaneously, makes precipitation supernatant direct reuse, has improved the yield of vanadium, has also improved the grade of vanadium oxide.
Thus, the invention provides a kind of purification process containing vanadium solution, it is characterized in that, the method comprises and will contact with acid cation exchange resin containing vanadium solution, carry out cation exchange, and the vanadium solution that contains after contact being separated with acid cation exchange resin, the described isopolyacid radical ion that contains metal cation and vanadium containing vanadium solution.
The present invention also provides a kind of preparation method of ammonium metavanadate, the method comprises carries out purifying by the vanadium solution of the isopolyacid radical ion containing vanadium, and the vanadium solution pH value conditioning agent that contains that purifying is obtained regulates pH value to contact with ammonium precipitating reagent after being less than or equal to 9 for being greater than 7.5, obtain ammonium metavanadate precipitation, it is characterized in that, the method that the described vanadium solution by the isopolyacid radical ion containing vanadium carries out purifying is the above-mentioned purification process containing vanadium solution.
The present invention also provides a kind of preparation method of vanadium oxide, and the method comprises prepares ammonium metavanadate, and by ammonium metavanadate roasting, it is characterized in that, the preparation method that the described method of preparing ammonium metavanadate is above-mentioned ammonium metavanadate provided by the invention.
The acid cation exchange resin using due to the purification process containing vanadium solution provided by the invention does not adsorb the isopolyacid radical ion containing the vanadium in vanadium solution, and exchange with the easily exchanged metal cation such as potassium, sodium, therefore can process the vanadium solution that contains of high concentration.In addition, because resin cation has adsorbed containing sodium ion, potassium ion and other cation in vanadium solution, make sodium ion, potassium ion and other cationic content containing in vanadium solution after ion-exchange considerably less, in addition, in the present invention, in the time of adjust pH, just adopt ammoniacal liquor, and in existing technique, entirely add ammonium sulfate, this point has reduced the addition of sulphur, finally can obtain potassium, sodium, low, the high-grade vanadium oxide of sulfur content.
In sum, method of the present invention, compared with existing precipitation technology, has following significantly advantage:
1, can process high concentration containing vanadium solution;
2, precipitation time adopts low ammonium precipitation, and adding ammonium coefficient (taking ammonium sulfate) is 1-1.3, and low, the low salinity of ammonia nitrogen concentration in precipitation supernatant can direct reuse, has improved the yield of vanadium;
3, potassium in vanadium oxide, sodium, sulfur content are low, have improved product grade.
Detailed description of the invention
The invention provides a kind of purification process containing vanadium solution, it is characterized in that, the method comprises and will contact with acid cation exchange resin containing vanadium solution, carry out cation exchange, and make to separate with acid cation exchange resin containing vanadium solution the described isopolyacid radical ion that contains metal cation and vanadium containing vanadium solution.
Because the purification process containing vanadium solution of the present invention is by making containing the metal cation in vanadium solution and the hydrogen ion generation ion-exchange in acid cation exchange resin, therefore described acid cation exchange resin can be various acid cation exchange resins, as long as can realize above-mentioned functions.Under preferable case, described acid cation exchange resin is storng-acid cation exchange resin.More preferably strongly acidic styrene type cation exchange resin.
Purification process containing vanadium solution of the present invention, wherein, the total exchange capacity of described acid cation exchange resin is 4.35mmol H
+/ gram-5mmol H
+/ gram.
A preferred embodiment of the invention, the described mode contacting with acid cation exchange resin containing vanadium solution is for making the described vanadium solution that contains by acid cation exchange resin bed, and the described time contacting with cationic ion-exchange resin containing vanadium solution is 1-50min.
Because the purification process containing vanadium solution of the present invention is to realize by making to carry out ion-exchange containing the metal cation in vanadium solution and acid cation exchange resin, therefore have no particular limits containing the metal cation concentration in vanadium solution, as long as meet the condition of ion-exchange, particularly.Can be to be 0-5 mol/L in the concentration that contains metal cation in vanadium solution.Should be containing vanadium solution by the concentration containing metal cation in vanadium solution after acid cation exchange resin bed lower than 0.054 mol/L.Described metal cation comprises sodium ion and/or potassium ion.
As previously mentioned, the purification process containing vanadium solution of the present invention can be processed the vanadium solution that contains compared with prior art higher concentration, and particularly, in v element, the described concentration containing vanadium in vanadium solution can be 10-100 grams per liter, is preferably 40-60 grams per liter.
According to the purification process containing vanadium solution of the present invention, wherein, described can be the vanadium solution that contains in various sources containing vanadium solution, and the present invention is preferably the vanadium solution that contains by sodium roasting-water logging explained hereafter.
The present invention also provides a kind of preparation method of ammonium metavanadate, the method comprises carries out purifying by the vanadium solution of the isopolyacid radical ion containing vanadium, and the vanadium solution pH value conditioning agent that contains that purifying is obtained regulates pH value to contact with ammonium precipitating reagent after being less than or equal to 9 for being greater than 7.5, obtain ammonium metavanadate precipitation, it is characterized in that, the method that the described vanadium solution by the isopolyacid radical ion containing vanadium carries out purifying is the above-mentioned purification process containing vanadium solution.
Above-mentioned pH value conditioning agent can be various pH value conditioning agent known in the field, and the present invention is preferably one or more in liquefied ammonia, ammoniacal liquor, carbonic hydroammonium and ammonium carbonate.
According to the preparation method of above-mentioned ammonium metavanadate, wherein, described ammonium precipitating reagent can be one or more in ammonium sulfate, ammonium chloride, carbonic hydroammonium, ammonium carbonate, liquefied ammonia and ammoniacal liquor.
According to the preparation method of above-mentioned ammonium metavanadate, wherein, adding ammonium coefficient can be 1-1.3, is preferably 1-1.2.The described ammonium coefficient (in ammonium sulfate) that adds, calculates in the following manner:
G＝K
NH4 +.V.C
G is ammonium sulfate addition, and unit is kg; V is the volume of solution, and unit is m
3; C is the concentration containing vanadium solution in v element, and unit is kg/m
3; KNH4+ is for adding ammonium coefficient.In the present invention because metal cation in vanadium solution is adsorbed by acid cation exchange resin, in vanadium solution, metal cation is few, the ammonia adding is just directly combined with vanadium, does not need the ammonia content of adding in ammonium salt raising solution to go to compete, replace with other cation, therefore adds ammonium coefficient little.Owing to adding, ammonium coefficient is little, and low, the low salinity of ammonia nitrogen concentration in precipitation supernatant can direct reuse, has improved the yield of vanadium.
The present invention also provides a kind of preparation method of vanadium oxide, and the method comprises prepares ammonium metavanadate, and by ammonium metavanadate roasting, it is characterized in that, the preparation method that the described method of preparing ammonium metavanadate is above-mentioned ammonium metavanadate.The condition of described roasting can be condition known in the field, and for example: sintering temperature can be 500-600 DEG C, roasting time can be 6-8 hour.After cooling, obtain highly purified vanadic anhydride.
In the present invention, precipitation rate refers to vanadium content and the ratio that precipitates vanadium content total in front solution in the sediment obtaining after vanadium precipitation.
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
The large hole strong acid styrene system cation exchange resin (D001 large hole strong acid styrene system cation exchange resin, the exchange capacity>=4.35mmolH that are 1000g by weight containing vanadium solution by 2L containing sodium roasting-water logging explained hereafter of 40 DEG C of vanadium 40.46g/L, sodium 31.5g/L, potassium 0.64g/L, temperature
+/ gram, resin Science and Technology Ltd. borders on the sea in Jiangsu Province) bed, be 2min containing vanadium solution with the swap time that contacts of ion exchange resin, after exchange, in vanadium solution, contain vanadium 40.25g/L, sodium 1.23g/L, potassium < 0.01g/L, pH=1.05, to exchange after vanadium solution in add ammoniacal liquor regulate pH to 7.5, add carbonic hydroammonium to carry out precipitation, it is 1 that control adds ammonium coefficient (taking ammonium sulfate) again, and precipitation rate is 77.2%.By after the ammonium metavanadate filtration washing being settled out in electric forge furnace at 500-600 DEG C calcination 6-8 hour, obtain vanadic anhydride product after cooling.In the vanadic anhydride product obtaining, contain V
2o
5: 99.58 % by weight, Na
2o < 0.01 % by weight, K
2o < 0.01 % by weight, S < 0.01 % by weight.
Comparative example 1
Add sulphur acid for adjusting pH to 7.5 by 2L containing sodium roasting-water logging explained hereafter of 40 DEG C of vanadium 40.46g/L, sodium 31.5g/L, potassium 0.64g/L, temperature containing vanadium solution, add again carbonic hydroammonium to carry out precipitation, controlling in vanadium solution cation, to add ammonium coefficient (taking ammonium sulfate) be 1, and precipitation rate is 15.8%.By after the ammonium metavanadate filtration washing being settled out in electric forge furnace at 500-600 DEG C calcination 6-8 hour, obtain vanadic anhydride product after cooling.In the vanadic anhydride product obtaining, contain V
2o
5: 98.25 % by weight, Na
2o:0.60 % by weight, K
2o:0.21 % by weight, S:0.30 % by weight.
Embodiment 2
By 2L containing sodium roasting-water logging explained hereafter of vanadium 45.75g/L, sodium 29.3g/L, potassium 0.61g/L, temperature 50 C containing vanadium solution by large hole strong acid styrene system cation exchange resin (D001 large hole strong acid styrene system cation exchange resin, the exchange capacity>=4.35mmolH of 1000g
+/ gram, resin Science and Technology Ltd. borders on the sea in Jiangsu Province) bed, be 20min containing vanadium solution with the swap time that contacts of ion exchange resin, after exchange, in vanadium solution, contain vanadium 45.43g/L, sodium 0.51g/L, potassium < 0.01g/L, pH=1.03, to exchange after vanadium solution in add ammoniacal liquor regulate pH to 8.0, add carbonic hydroammonium to carry out precipitation, it is 1.2 that control adds ammonium coefficient (taking ammonium sulfate) again, and precipitation rate is 92.5%.By after the ammonium metavanadate filtration washing being settled out in electric forge furnace at 500-600 DEG C calcination 6-8 hour, obtain vanadic anhydride product after cooling.In the vanadic anhydride product obtaining, contain V
2o
5: 99.76 % by weight, Na
2o < 0.01 % by weight, K
2o < 0.01 % by weight, S < 0.01 % by weight.
Embodiment 3
By 2L containing sodium roasting-water logging explained hereafter of 30 DEG C of vanadium 57.38g/L, sodium 34.50g/L, potassium 0.67g/L, temperature containing vanadium solution by large hole strong acid styrene system cation exchange resin (D001 large hole strong acid styrene system cation exchange resin, the exchange capacity>=4.35mmolH of 1000g
+/ gram, resin Science and Technology Ltd. borders on the sea in Jiangsu Province) bed, be 50min containing vanadium solution with the swap time that contacts of ion exchange resin, after exchange, in vanadium solution, contain vanadium 56.86g/L, sodium 0.28g/L, potassium < 0.01g/L, pH=1.01, to exchange after vanadium solution in add ammoniacal liquor regulate pH to 8.5, add carbonic hydroammonium to carry out precipitation, it is 1.3 that control adds ammonium coefficient (taking ammonium sulfate) again, and precipitation rate is 98.2%.By after the ammonium metavanadate filtration washing being settled out in electric forge furnace at 500-600 DEG C calcination 6-8 hour, obtain vanadic anhydride product after cooling.In the vanadic anhydride product obtaining, contain V
2o
5: 99.85 % by weight, Na
2o < 0.01 % by weight, K
2o < 0.01 % by weight, S < 0.01 % by weight.
Embodiment 4
Carry out according to the scheme of embodiment 1, different is by large hole strong acid styrene system cation exchange resin replace with the equal hole of JK008 strongly acidic styrene type cation exchange resin (the equal hole of JK008 strongly acidic styrene type cation exchange resin, exchange capacity >=4.35mmolH+/gram, resin Science and Technology Ltd. borders on the sea in Jiangsu Province), in the vanadic anhydride product obtaining, contain V2O5:98.85 % by weight, Na2O:0.09 % by weight, K2O:0.02 % by weight, S < 0.01 % by weight.
Therefore, adopt method of the present invention can directly process high concentration containing vanadium solution; In the time of precipitation, adopt low ammonium precipitation, adding ammonium coefficient (taking ammonium sulfate) is 1-1.3; Potassium in vanadium oxide, sodium, sulfur content are low, have improved product grade.Therefore, method of the present invention is prepared vanadium oxide and is had yield and the vanadium product quality that simple easy operating, cost are low, improved vanadium, has brought good economic benefit and social benefit, has good application prospect.
Claims (11)
1. the preparation method of an ammonium metavanadate, the method comprises carries out purifying by the vanadium solution of the isopolyacid radical ion containing vanadium, and purifying is obtained regulate pH value to contact with ammonium precipitating reagent after being less than or equal to 9 for being greater than 7.5 containing vanadium solution pH value conditioning agent, obtain ammonium metavanadate and precipitate;
Wherein, the method for the vanadium solution of the isopolyacid radical ion containing vanadium being carried out to purifying is made up of following process: will contact with acid cation exchange resin containing vanadium solution, and carry out ion-exchange, and make separating with acid cation exchange resin containing vanadium solution after contact; Wherein, described is the vanadium solution that contains by sodium roasting-water logging explained hereafter containing vanadium solution, the described isopolyacid ion that contains metal cation and vanadium containing vanadium solution, and described metal cation comprises sodium ion and/or potassium ion;
Wherein, when precipitation, adopt low ammonium precipitation, add ammonium coefficient and count 1-1.3 with ammonium sulfate;
Wherein, in v element, the described concentration containing vanadium in vanadium solution is 10-100 grams per liter.
2. method according to claim 1, wherein, pH value conditioning agent is one or more in liquefied ammonia, ammoniacal liquor, carbonic hydroammonium and ammonium carbonate; Described ammonium precipitating reagent is one or more in ammonium sulfate, ammonium chloride, carbonic hydroammonium, ammonium carbonate, liquefied ammonia and ammoniacal liquor.
3. method according to claim 1, wherein, described acid cation exchange resin is storng-acid cation exchange resin.
4. method according to claim 3, wherein, described storng-acid cation exchange resin is strongly acidic styrene type cation exchange resin.
5. according to the method described in any one in claim 1,3 and 4, wherein, the total exchange capacity>=4.35mmolH of described acid cation exchange resin
+/ gram.
6. according to the method described in any one in claim 1,3 and 4, wherein, the total concentration that contains metal cation in vanadium solution after described condition contact with acid cation exchange resin containing vanadium solution makes to contact is lower than 0.054 mol/L.
7. method according to claim 6, wherein, the total exchange capacity>=4.35mmolH of described acid cation exchange resin
+/ gram.
8. method according to claim 6, wherein, the described time contacting with described acid cation exchange resin containing vanadium solution is 1-50min.
9. method according to claim 1, wherein, the described concentration containing metal cation in vanadium solution is for being greater than 0 and be less than or equal to 5 mol/L.
10. method according to claim 1, wherein, in v element, the described concentration containing vanadium in vanadium solution is 40-60 grams per liter.
The preparation method of 11. 1 kinds of vanadium oxides, the method comprises prepares ammonium metavanadate, and by ammonium metavanadate roasting, it is characterized in that, and the described method of preparing ammonium metavanadate is the method described in any one in claim 1-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8871163B2 (en) | 2012-09-18 | 2014-10-28 | American Vanadium Corp. | Vanadium oxide purification process |
| CN103708553B (en) * | 2013-12-26 | 2016-01-06 | 国药集团化学试剂有限公司 | A kind of method promoting technical grade ammonium meta-vanadate quality |
| CN104098137B (en) * | 2014-07-24 | 2016-08-17 | 福建福晶科技股份有限公司 | The preparation of a kind of ammonium metavanadate and purification process |
| CN104386747B (en) * | 2014-11-18 | 2016-03-30 | 河北钢铁股份有限公司承德分公司 | A kind of ion exchange method prepares the method for high purity barium oxide |
| CN106145188A (en) * | 2016-07-05 | 2016-11-23 | 河北钢铁股份有限公司承德分公司 | A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride |
| CN107298461A (en) * | 2017-08-17 | 2017-10-27 | 芜湖人本合金有限责任公司 | The method of purification of ammonium metavanadate and high-purity ammonium metavanadate |
| CN107285382A (en) * | 2017-08-17 | 2017-10-24 | 芜湖人本合金有限责任公司 | The preparation method of high purity vanadic anhydride |
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| CN1449299A (en) * | 2000-08-28 | 2003-10-15 | 亨克尔两合股份公司 | Method for separating multivalent metal ions |
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