CN103663557B - Method for preparing high-purity vanadium pentoxide from coarse vanadium - Google Patents
Method for preparing high-purity vanadium pentoxide from coarse vanadium Download PDFInfo
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- CN103663557B CN103663557B CN201410006301.5A CN201410006301A CN103663557B CN 103663557 B CN103663557 B CN 103663557B CN 201410006301 A CN201410006301 A CN 201410006301A CN 103663557 B CN103663557 B CN 103663557B
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Abstract
The invention provides a method for preparing high-purity vanadium pentoxide from coarse vanadium. The method comprises the steps that coarse vanadium is dissolved in caustic soda; the final pH value of dissolution is controlled to be 7 to 8.5; ferric hydroxide colloid is removed after static filtration; then hydrogen peroxide is added into the filtrate to oxidize, filter and remove the colloid; resin is exchanged by anion; after the resin is saturated, acid solution is used for analysis; analytical solution is added with ammonia molybdenum precipitation, vanadium pentoxide is produced, filtered and washed by pure water; the vanadium pentoxide is roasted to produce high-purity vanadium pentoxide with the purity of above 99.9 percent.
Description
Technical field
The present invention is the method for purification field belonging to Vanadium Pentoxide in FLAKES, is specifically related to a kind of method that thick vanadium prepares high purity vanadic anhydride.
Background technology
Vanadium is a kind of important resource, and because of the physics-chem characteristic that it is intrinsic, vanadium is widely used in the every field of national defence and economic construction.Current China vanadium industry development is rapid, and especially extracting vanadium from stone coal industry extraction Vanadium Pentoxide in FLAKES technique is constantly ripe, and novel process is constantly put in production process, impels China's vanadium industry output significantly to increase.
Current vanadium industry production enterprise of China common product is 98 vanadium, and namely in product, pentoxide content is 98%, and this product is the low-end product of vanadium industry, is generally used as the additive of steel industry, belongs to traditional Application Areas.Along with the expansion that vanadium is applied at other field, as at aerospace material, in the application process of special steel material and alloy, it is strict to the control overflow of impurity element, therefore also more and more higher to the purity requirement of vanadium product, the research for the preparation method of high purity vanadium seems particularly important.The method of purification Vanadium Pentoxide in FLAKES conventional at present has the removal of impurities of the chemical precipitation method of purification, solvent extration removal of impurities and ion exchange method removal of impurities.
The production of high purity vanadic anhydride, domesticly at present mostly adopts the cleaners such as Tai-Ace S 150, calcium chloride, oxalic acid, sulphosalicylic acid, reduces the content of silicon in vanadium, phosphorus, iron respectively in different pH value.Its technical process is long, and work consuming is many, and production cost is high, and Vanadium Pentoxide in FLAKES product purity does not all reach the requirement of some high-end product vanadium mostly.
Summary of the invention
The defects such as the technical problem that the present invention mainly solves is, cost in existing high purity vanadic anhydride preparation process is high in order to overcome, technical sophistication, technical process are long, and raw materials consumption is high, are intended to propose a kind of method preparing high purity vanadic anhydride from thick vanadium.It adopts comparatively simple technique, mainly through techniques such as caustic soda dissolving, iron removal by oxidation, ion-exchanges, simplifies preparation technology's flow process, decreases operation, improve the quality of products.
For achieving the above object, technical scheme of the present invention is:
Thick vanadium prepares a method for high purity vanadic anhydride, and the method comprises the following steps:
1) thick vanadium ore grinding is extremely Powdered, make powder size be less than 0.15mm, obtain thick vanadium powder end; Described thick vanadium purity > 98%; Described thick vanadium powder end is added in the sodium hydroxide solution of 1mol/L ~ 3mol/L, stir, control whipping temp 30 DEG C ~ 80 DEG C, along with adding of thick vanadium powder end, Vanadium Pentoxide in FLAKES dissolves gradually, the pH value of solution constantly reduces, be the terminal adding thick vanadium powder end during control pH value of solution to 7 ~ 8.5, after reaching terminal, stir 1.0h-1.5h again, then terminate to stir, leave standstill 10 h ~ 30h, obtain thick vanadium solution;
2) described thick vanadium solution is filtered, the not molten material in removing solution and ferric hydroxide colloid; Add hydrogen peroxide 5mL ~ 40mL again and be oxidized 10 h ~ 30h, obtain oxidizing solution; The add-on of described hydrogen peroxide is 2-3 times of the molar weight of iron in described thick vanadium solution; Filtered by described oxidizing solution, the ferric hydroxide colloid produced in removing oxidizing solution, obtains the oxidizing solution after filtration;
3) the oxidizing solution deionized water after described filtration is diluted, make V in solution
2o
5concentration is that 50 g/L ~ 80g/L are as the criterion, and obtains diluent; Described diluent is crossed anionite-exchange resin absorption, after saturated to anionite-exchange resin, stop ionic adsorption;
4) with pH be 2.0 ~ 2.5 hydrochloric acid soln washing saturated after anionite-exchange resin, until it is 7.0 ~ 7.5 that resin flows out the pH of solution, then with the deionized water wash resin relative to resin volume 5 ~ 8 times, to resin washings without color;
5) use the hydrochloric acid soln of 2.8mol/L-3.2mol/L as ion desorbed solution again, described ion exchange resin is resolved, resolve before returning to absorption to color of resin, obtain the desorbed solution containing Vanadium Pentoxide in FLAKES 60g/L ~ 100g/L;
6) described desorbed solution is added hydrogen peroxide oxidation, by weight, every 100 parts of desorbed solutions add 1mL ~ 10mL hydrogen peroxide to hydrogen peroxide add-on, then adjust pH to 2 ~ 2.5 with ammoniacal liquor, heat to 90 DEG C ~ 95 DEG C, and insulation 2h ~ 3.0h, filters, obtain throw out; Wash 3 ~ 5 times with the deionization relative to throw out 3 ~ 5 times of volumes, obtain the throw out after washing;
7) throw out after washing is calcined 2.5 h ~ 3.0h under 500 DEG C ~ 550 DEG C conditions, obtain the Vanadium Pentoxide in FLAKES that purity is greater than 99.9%.
The described thick vanadium of step (1) is preferably 98 vanadium, mainly becomes as V
2o
5> 98%, Si < 0.2%, Fe < 0.3%, P < 0.05%, S < 0.03%, As < 0.02%, Na
2o+ K
2o < 1.5%, total impurities content < 2%.
Step (4) described anionite-exchange resin is preferably D318 type resin anion(R.A) exchange resin.
The hydrogen peroxide of step (2) and the hydrogen peroxide described in step (6) to be mass concentration be 20%-30%, is more preferably the hydrogen peroxide that mass concentration is 30%.
The present invention will be further explained below:
High purity vanadic anhydride of the present invention refers to that purity is more than or equal to the Vanadium Pentoxide in FLAKES of 99.9%.
Of the present inventionly prepare thick vanadium solution in high purity vanadium method and adopt caustic soda soln, hydrogen peroxide oxidation is used to produce ferric hydroxide colloid deep iron removal, removing ferric hydroxide colloid is used containing colloidal solution, use the resin anion(R.A) exchange adsorption vanadium such as D318, realize being separated of vanadium and iron ion and sodium ion, and then output high purity vanadic anhydride.
The thick vanadium of the present invention prepares the method for high purity vanadic anhydride, preferably using raw material for meeting 98 vanadium of People's Republic of China (PRC) ferrous metallurgy industry standard " Vanadium Pentoxide in FLAKES " (YB/T5304-2011), mainly becoming as V
2o
5> 98%, Si < 0.2%, Fe < 0.3%, P < 0.05%, S < 0.03%, As < 0.02%, Na
2o+ K
2o < 1.5%, total impurities content < 2%.The method comprises the following steps:
Get a certain amount of thick vanadium (containing V
2o
598%), require that thick vanadium is powder, granularity is less than 0.15mm.Sodium hydroxide deionized water is mixed with the solution of 1 ~ 3mol/L.Powdered 98 vanadium are slowly added, mechanical stirring, holding temperature 30 ~ 80 DEG C in sodium hydroxide solution.Along with thick vanadium adds, Vanadium Pentoxide in FLAKES dissolves gradually, and the pH value of solution constantly reduces, and controls solution terminal pH7 ~ 8.5.Reach mechanical stirring 1.0h after terminal.Stirring terminates rear standing 10 ~ 30h.Present blackish green in thick vanadium solution process, after leaving standstill, present garnet.
Primary chemical principle: V
2o
5+ 2NaOH=2NaVO
3+ H
2o
Thick vanadium solution after leaving standstill filters, and filters and adopts accurate filter paper filtering, not molten to material and most ferric hydroxide colloid in removing solution.Add 5 ~ 40mL hydrogen peroxide according to vanadium in solution and concentration of iron, oxidation 10 ~ 30h, occur White Flocculus bottom solution container after oxidation leaves standstill, main component is ironic hydroxide.Filter, a small amount of ferric hydroxide colloid produced in removing oxidizing solution.
Oxidising process: 2H
++ Fe
2++ H
2o
2=Fe
3++ 2H
2o
Fe
3++3OH
-=Fe(OH)
3↓
Oxidizing solution deionized water after filtration is diluted to V
2o
5concentration is 50 ~ 80g/L, and slowly add through anionite-exchange resin such as pretreated D318, absorption flow is according to V
2o
5concentration controls, V in liquid after ion-exchange
2o
5concentration is generally 0.3 ~ 0.5g/L, after waiting until that exchange resin is saturated, stops ionic adsorption.
Be the hydrochloric acid soln washing of 2.0 ~ 2.5 by the ion exchange resin pH after saturated, until the pH that resin flows out solution is 7.0 ~ 7.5.With the deionized water wash resin of resin volume 5 ~ 8 times, guarantee that the solution flowed out from resin is without color.
3mol/L hydrochloric acid soln is prepared as ion desorbed solution with analytical pure hydrochloric acid and deionized water.Ion exchange resin obtains containing Vanadium Pentoxide in FLAKES 60 ~ 100g/L solution before resolving and returning to absorption to color of resin.
Precipitation: desorbed solution adds hydrogen peroxide oxidation, add-on adds 1 ~ 10mL hydrogen peroxide according to every 100 parts of desorbed solutions, then adjusts pH value of solution 2 ~ 2.5 with analytical pure ammoniacal liquor; Heat to 90 ~ 95 DEG C, maintain 2 ~ 3.0h and obtain redness or garnet throw out, the red vanadium of output after filtering, with the deionized water drip washing 3 ~ 5 times of sediment volume 3 ~ 5 times.
Red vanadium calcining: the throw out after washing is calcined 2.5 ~ 3.0h under 500 ~ 550 DEG C of conditions, obtains pulverous high purity vanadic anhydride.
Compared with prior art, advantage of the present invention is:
1, the present invention overcomes that cost in existing high purity vanadic anhydride preparation process is high, technical sophistication, technical process be long, and the defects such as raw materials consumption is high, provide a kind of method preparing high purity vanadic anhydride.
2, of the present inventionly prepare thick vanadium solution in high purity vanadium method and adopt caustic soda soln, hydrogen peroxide oxidation is used to produce ferric hydroxide colloid deep iron removal, removing ferric hydroxide colloid is used containing colloidal solution, use the resin anion(R.A) exchange adsorption vanadium such as D318, realize being separated of vanadium and iron ion and sodium ion, thus obtaining high purity vanadic anhydride, technique is simple.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that in the embodiment of the present invention, thick vanadium prepares high purity vanadic anhydride.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
embodiment 1
Get the caustic soda soln of 1.0L1mol/L deionized water preparation, slowly add thick Vanadium Pentoxide in FLAKES wherein, and constantly stir, maintain whipping temp 40 DEG C, control pH value of solution most 8 ~ 9, add thick vanadium 142.5g altogether, solution terminal pH is 8.4.Solution once thought sap green, and leave standstill 24h and filter, filtrate presents redness.
In filtrate, add 10mL hydrogen peroxide, leave standstill 20h, in solution, occur that a small amount of White Flocculus is deposited in bottom solution, filter, the vanadium solution that output is high-purity.
With deionized water diluting soln to being wherein 80g/L containing vanadium concentration, obtain in the exchange resin that solution 1.35L joins containing 300gD318 resin, controls flow is 0.5h/L, and solution circulated is adsorbed until resin is saturated and present golden yellow.Resin is with deionized water wash to neutral, and namely flowing out wash water pH in resin is 7.0.
With the 3mol/L hydrochloric acid soln 1L that deionized water and hydrochloric acid are prepared, slow transit through saturated resin, resolve the vanadium in resin, obtain containing Vanadium Pentoxide in FLAKES 90g/L solution.
Add 20mL hydrogen peroxide (mass concentration is 30%) oxidation 0.5h to desorbed solution 1.0L, constantly stir in oxidising process, then adjust pH value of solution 2.0 with analytical pure ammoniacal liquor; Heat to 90 ~ 95 DEG C, maintain 2.0h and obtain garnet throw out, the red vanadium of output after filtering, with the deionized water drip washing 3 times of sediment volume 3 times.
Red vanadium calcining: the throw out after washing is calcined 2.5 ~ 3.0h under 500 ~ 550 DEG C of conditions, obtains pulverous high purity vanadic anhydride, containing Vanadium Pentoxide in FLAKES 99.93%.
embodiment 2
Get the caustic soda soln of 1.0L2.0mol/L deionized water preparation, slowly add thick Vanadium Pentoxide in FLAKES wherein, and constantly stir, maintain whipping temp 60 DEG C, control pH value of solution most 7 ~ 8, add thick vanadium 290g altogether, solution terminal pH is 7.5.Solution once thought garnet, left standstill 24h and filtered.
In filtrate, add 30mL hydrogen peroxide, leave standstill 28h, in solution, occur that White Flocculus is deposited in bottom solution, filter, the vanadium solution that output is high-purity.
With deionized water diluting soln to being wherein 90g/L containing vanadium concentration, obtain in the exchange resin that solution 2.90L joins containing D318 resin, controls flow is 0.5h/L, and solution circulated is adsorbed until resin is saturated and present golden yellow.Resin is first 7.0 with flowing out pH value of solution in the analytical pure hydrochloric acid soln drip washing to resin of pH2.5.Extremely neutral with deionized water wash again, namely flowing out wash water pH in resin is 7.0.
With the 3mol/L hydrochloric acid soln 1.5L that deionized water and hydrochloric acid are prepared, slow transit through saturated resin, resolve the vanadium in resin, obtain containing Vanadium Pentoxide in FLAKES 105g/L solution.
Add 40mL hydrogen peroxide (mass concentration is 30%) oxidation 1.0h to desorbed solution 1.5L, constantly stir in oxidising process, then adjust pH value of solution 2.0 with analytical pure ammoniacal liquor; Heat to 90 ~ 95 DEG C, maintain 1.5h and obtain garnet throw out, the red vanadium of output after filtering, with the deionized water drip washing 4 times of sediment volume 5 times.
Red vanadium calcining: the throw out after washing is calcined 2.5 ~ 3.0h under 500 ~ 550 DEG C of conditions, obtains pulverous high purity vanadic anhydride, containing Vanadium Pentoxide in FLAKES 99.99%.
Claims (3)
1. thick vanadium prepares a method for high purity vanadic anhydride, it is characterized in that, the method comprises the following steps:
1) thick vanadium ore grinding is extremely Powdered, make powder size be less than 0.15mm, obtain thick vanadium powder end; Described thick vanadium purity > 98%; Described thick vanadium powder end is added in the sodium hydroxide solution of 1mol/L ~ 3mol/L, stir, control whipping temp 30 DEG C ~ 80 DEG C, along with adding of thick vanadium powder end, Vanadium Pentoxide in FLAKES dissolves gradually, the pH value of solution constantly reduces, be the terminal adding thick vanadium powder end during control pH value of solution to 7 ~ 8.5, after reaching terminal, stir 1.0h-1.5h again, then terminate to stir, leave standstill 10h ~ 30h, obtain thick vanadium solution;
2) described thick vanadium solution is filtered, the not molten material in removing solution and ferric hydroxide colloid; Add hydrogen peroxide 5mL ~ 40mL again and be oxidized 10h ~ 30h, obtain oxidizing solution; The add-on of described hydrogen peroxide is 2-3 times of the molar weight of iron in described thick vanadium solution; Filtered by described oxidizing solution, the ferric hydroxide colloid produced in removing oxidizing solution, obtains the oxidizing solution after filtration;
3) the oxidizing solution deionized water after described filtration is diluted, make V in solution
2o
5concentration is that 50g/L ~ 80g/L is as the criterion, and obtains diluent; Described diluent is crossed anionite-exchange resin absorption, after saturated to anionite-exchange resin, stop ionic adsorption;
4) with pH be 2.0 ~ 2.5 hydrochloric acid soln washing saturated after anionite-exchange resin, until it is 7.0 ~ 7.5 that resin flows out the pH of solution, then with the deionized water wash resin relative to resin volume 5 ~ 8 times, to resin washings without color; Described anionite-exchange resin is D318 type anionite-exchange resin;
5) use the hydrochloric acid soln of 2.8mol/L-3.2mol/L as ion desorbed solution again, described ion exchange resin is resolved, resolve before returning to absorption to color of resin, obtain the desorbed solution containing Vanadium Pentoxide in FLAKES 60g/L ~ 100g/L;
6) described desorbed solution is added hydrogen peroxide oxidation, by weight, every 100 parts of desorbed solutions add 1mL ~ 10mL hydrogen peroxide to hydrogen peroxide add-on, then adjust pH to 2 ~ 2.5 with ammoniacal liquor, heat to 90 DEG C ~ 95 DEG C, and insulation 2h ~ 3.0h, filters, obtain throw out; Wash 3 ~ 5 times with the deionization relative to throw out 3 ~ 5 times of volumes, obtain the throw out after washing;
7) throw out after washing is calcined 2.5h ~ 3.0h under 500 DEG C ~ 550 DEG C conditions, obtain the Vanadium Pentoxide in FLAKES that purity is greater than 99.9%.
2. thick vanadium prepares the method for high purity vanadic anhydride according to claim 1, and it is characterized in that, the described thick vanadium of step (1) is 98 vanadium, mainly becomes as V
2o
5> 98%, Si < 0.2%, Fe < 0.3%, P < 0.05%, S < 0.03%, As < 0.02%, Na
2o+K
2o < 1.5%, total impurities content < 2%.
3. according to claim 1 or 2, thick vanadium prepares the method for high purity vanadic anhydride, it is characterized in that, the hydrogen peroxide of step (2) and the hydrogen peroxide described in step (6) to be mass concentration be 20%-30%.
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| 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 |
| CN105984899B (en) | 2015-01-30 | 2017-05-17 | 中国科学院过程工程研究所 | System and method for purifying vanadium pentoxide |
| CN105984896B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of purification prepares the system and method for high purity vanadic anhydride powder |
| CN105984897B (en) | 2015-01-30 | 2017-05-17 | 中国科学院过程工程研究所 | System and method for producing high-purity vanadium pentoxide powder |
| CN105984898B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of system and method for producing high-purity vanadium tetraoxide powder |
| CN105984900B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of system and method for preparing high purity vanadic anhydride powder |
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| EP1511691B1 (en) * | 2002-05-31 | 2007-01-03 | Highveld Steel & Vanadium Corporation Limited | Process for the preparation of vanadyl sulfate solution |
| CN101760651A (en) * | 2010-03-04 | 2010-06-30 | 中南大学 | Process for extracting vanadium by acid leaching of stone coal |
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