CN102910674A - Method for preparing calcium vanadate from phosphorus-removing underflow slag - Google Patents
Method for preparing calcium vanadate from phosphorus-removing underflow slag Download PDFInfo
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- CN102910674A CN102910674A CN2011102196836A CN201110219683A CN102910674A CN 102910674 A CN102910674 A CN 102910674A CN 2011102196836 A CN2011102196836 A CN 2011102196836A CN 201110219683 A CN201110219683 A CN 201110219683A CN 102910674 A CN102910674 A CN 102910674A
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- leach liquor
- aqueous solution
- underflow slag
- vanadium
- alkaline aqueous
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Abstract
The invention provides a method for preparing calcium vanadate from phosphorus-removing underflow slag. The method comprises the steps that: (1) the phosphorus-removing underflow slag contacts an alkaline aqueous solution, and the obtained material is subjected to solid-liquid separation, such that a leaching solution is obtained; (2) the leaching solution obtained in the step (1) contacts a silicon-removing agent and is subjected to silicon removing, such that a silicon-removed leaching solution is obtained; and (3) under an alkaline condition, the silicon-removed leaching solution obtained in the step (2) contacts a soluble calcium salt, such that calcium vanadate is obtained. With the calcium vanadate preparation method provided by the invention, a vanadium recovery rate of the calcium vanadate is high, and the process is simple.
Description
Technical field
The present invention relates to a kind of method that is prepared vanadic acid calcium by dephosphorization underflow slag.
Background technology
Produce in the production technique of vanadium oxide at traditional vanadium slag sodium roasting, for obtaining the higher vanadium oxide product of purity, the sodium roasting product is carried out after the water logging, need to carry out removal of impurities to impurity such as the silicon in the leach liquor, phosphorus, common impurity-removing method is to add calcium hydroxide to produce precipitation in leach liquor, the solid matter of gained is dephosphorization underflow slag, the impurity such as the phosphorus in the leach liquor and silicon just enter into dephosphorization underflow slag like this, carried simultaneously a large amount of vanadium and arrived wherein, wherein content of vanadium is generally the 10-20 % by weight.In order to improve the utilization ratio of vanadium, traditional way is dephosphorization underflow slag to be returned multiple hearth furnace carry out re-baking, like this, although make vanadium obtain recovery, wherein calcium contents is high, can reduce roasting efficient, simultaneously, from dephosphorization underflow slag, remove the impurity such as phosphorus and silicon and also have larger difficulty, virtually increased production cost, and the rate of recovery of vanadium from dephosphorization base flow residues is not high yet.
For example, CN101182037A discloses a kind of method that metavanadic acid ammonia or many vanadic acid ammonia obtain vanadium oxide of producing after dephosphorization underflow slag is leached by carbonate solution, and its technical process is brief, has realized the recycle of waste water, but its vanadium recovery is relatively low, and product also is traditional vanadium oxide.
And for example, CN101100720A discloses a kind of production technique of smelting vanadium iron from calcium vanadate, wherein, vanadic acid calcium, aluminium powder, irony material smelted according to a certain weight ratio obtains vanadium iron: vanadic acid calcium: 100 parts, and aluminium powder: 23-28 part, irony material: 23-27 part; Wherein, described vanadic acid calcium is at least a in metavanadic acid calcium, pyrovanadic acid calcium, the positive vanadic acid calcium, and it contains the vanadium grade is 24%-43%.The vanadium iron quality that the method is smelted is good, does not produce contaminated wastewater in the smelting process, adapts to the infant industry needs that high economic worth, low environment are polluted, for the applications expanding of vanadic acid calcium the field.
" artificial lens journal " 26 volume 3-4 phases, in the growth and polarization of positive vanadic acid calcium crystal, utilize solid-state CaCO
3And V
2O
5Produce vanadic acid calcium, from its raw material, need to obtain first V
2O
5After use again the pressure cake of press of 200MPa (200kgf/cm2), at 1000 ℃ of lower sintering 3h, use the platinum crucible charge, 20kW, vanadic acid calcium is produced in ℃ fusing of TDK type single crystal growing furnace ratio-frequency heating to 1400, and this method can obtain the higher vanadic acid calcium of purity, but its energy consumption is high, equipment requirements is high, is difficult to realize industrialization.
Summary of the invention
The object of the present invention is to provide the preparation method of the simple new vanadic acid calcium of a kind of rate of recovery that can realize higher vanadium, preparation technology.
The inventor finds, contacts with dephosphorization underflow slag by adopting alkaline aqueous solution, has reduced the foreign matter content in the leach liquor that obtains, reduced the difficulty of removal of impurities, the leaching yield of vanadium is improved in the leach liquor, thereby has improved the rate of recovery of vanadium, thereby can obtain highly purified vanadic acid calcium product.
In order to achieve the above object, the invention provides and a kind ofly produce the method for vanadic acid calcium by dephosphorization underflow slag, the method comprises the steps:
1) dephosphorization underflow slag is contacted with alkaline aqueous solution and carry out solid-liquid separation, obtain leach liquor;
2) with step 1) leach liquor that obtains contacts with desiliconizing agent and carries out silica removal, obtains the leach liquor behind the silica removal;
3) under alkaline condition, with step 2) leach liquor behind the silica removal that obtains contacts with soluble calcium salt, obtains vanadic acid calcium.
Adopt the rate of recovery of vanadium of the vanadic acid calcium that the preparation method of vanadic acid calcium of the present invention obtains high, and technique is simple, can realize industrialization production.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, step 1) in, the feeding quantity of described alkaline aqueous solution can change within a large range, if can so that the vanadium in the described dephosphorization underflow slag fully leach, under the preferable case, take every gram dephosphorization underflow slag as benchmark, the feeding quantity of described alkaline aqueous solution is 1-10mL; More preferably, the feeding quantity of described alkaline aqueous solution is 1-5mL; Most preferably, the feeding quantity of described alkaline aqueous solution is 2-4mL.
According to the present invention, in step 1) in, the concentration of alkali can change in a big way in the described alkaline aqueous solution, under the preferable case, in order to realize the leaching of more efficient vanadium, the concentration of described alkaline aqueous solution can be the 10-90 % by weight, more preferably, and the concentration 20-80 % by weight of described alkaline aqueous solution; Most preferably, the concentration 40-60 % by weight of described alkaline aqueous solution.
According to the present invention, in step 1) in, described alkaline aqueous solution can be various alkaline aqueous solutions, and for example, the alkaline matter in the alkaline aqueous solution can be selected from one or more in sodium hydroxide, potassium hydroxide, sodium oxide, sodium peroxide, potassium oxide and the Potassium peroxide; More preferably in the situation, the alkaline matter in the described alkaline aqueous solution is sodium hydroxide and/or potassium hydroxide.
According to the present invention, in step 1) in, described contact conditions is not particularly limited, as long as can fully leach vanadium in the dephosphorization underflow slag; The condition of described contact generally comprises the temperature and time of contact, and is preferred, for the vanadium in the abundant leaching dephosphorization underflow slag to reach the transformation efficiency effect of further raising vanadium, the temperature of described contact is 30-200 ℃, be 20-400min duration of contact; More preferably, described Contact Temperature is 50-150 ℃, and be 30-200min duration of contact; Consider efficient and cost, most preferably, described Contact Temperature is 60-100 ℃, and be 40-120min duration of contact.
According to the present invention, in step 1) in, the mode that contacts of described dephosphorization underflow slag and described alkaline aqueous solution can be any way of contact well known in the art, for example, drip washing is under the preferable case, considering cost and effect, can be that dephosphorization underflow slag is mixed with alkaline aqueous solution, for example, preferably to adopt alkaline aqueous solution that dephosphorization underflow slag is flooded.In order to obtain better mixed effect, preferably under agitation, dephosphorization underflow slag and alkaline aqueous solution are mixed.Under the preferable case, in order to be easy to solid-liquid separation after mixing, can also carry out standing sedimentation.The method of described solid-liquid separation can be method known in those skilled in the art, for example, and the methods such as gravity settling, filtration, centrifugation.
According to the present invention, step 1) in, described dephosphorization underflow slag re-uses after can directly using or be ground into certain particle size, and in order to improve the leaching rate of vanadium, preferred, the particle diameter of described dephosphorization underflow slag is the 40-125 micron; More preferably in the situation, the particle diameter of described dephosphorization underflow slag is the 75-125 micron.
According to the present invention, step 1) in, described dephosphorization underflow slag is that vanadium slag sodium roasting product carries out after the water logging, add calcium hydroxide in the leach liquor and produce precipitation, the leach liquor of vanadium is carried out the solid matter that obtains after the removal of impurities, its main component: TV (total vanadium)/9.50-11.50 % by weight, the Si/4.50-5.50 % by weight, the P/0.40-0.80 % by weight, Mn/4.20-5.35 % by weight, Ca/7.50-9.50 % by weight.
According to the present invention, in step 2) in, described desiliconizing agent can be the conventional various any materials that silicon ion in the leach liquor that obtains can be removed and do not produced with calcium ion and/or chlorion precipitation that use in this area, preferred, described desiliconizing agent is selected from AlCl
3, FeCl
3Mg (NO
3)
2In one or more; AlCl more preferably
3And/or Mg (NO
3)
2, most preferably, described desiliconizing agent is AlCl
3
According to the present invention, the add-on of described desiliconizing agent can change within a large range, as long as it is just passable to remove as much as possible silicon ion contained in the leach liquor, but for cost consideration, preferably, the add-on of described desiliconizing agent is as the criterion with silicone content in the leach liquor, counts in molar ratio, and the positively charged ion in the desiliconizing agent is (such as Al
3+): Si
4+=1-10: 1; More preferably, the positively charged ion in the desiliconizing agent is (such as Al
3+): Si
4+=1-5: 1; Most preferably, the positively charged ion in the desiliconizing agent is (such as Al
3+): Si
4+=1-3: 1.
According to the present invention, in step 2) in, the mode of contact can be any way of contact well known in the art, for example can be that described leach liquor and desiliconizing agent are mixed, in order to obtain better mixed effect, preferably under agitation, described leach liquor and desiliconizing agent are mixed; Under the preferable case, in order to be easy to solid-liquid separation after mixing, can also carry out standing sedimentation.There is no particular limitation duration of contact for described leach liquor and desiliconizing agent, can guarantee that silicon ion in the leach liquor all removes just passablely, considers the effect of silica removal and the problem of production cycle, and preferably, described leach liquor and desiliconizing agent duration of contact are 1-10 hour; More preferably, be 2-8 hour described duration of contact, and most preferably, be 2-5 hour described duration of contact.
According to the present invention, in step 3) in, described alkaline condition refers to the pH of leaching solution behind the silica removal is adjusted to alkalescence, the method of the pH of the leach liquor behind the adjusting silica removal is conventionally known to one of skill in the art, for example, add acid or alkali and regulate, the concentration of acid or alkali and consumption can be adjusted according to actual needs, as long as guarantee the pH value of the leach liquor behind the silica removal is adjusted to 9-12, be preferably 10-11 and get final product.
According to the present invention, in step 3) in, the add-on of described soluble calcium salt can in very large range change, as long as it is just passable to guarantee all to transfer the vanadium ion in the solution to precipitation, consider cost and vanadium deposition rate, preferred, be as the criterion with content of vanadium in the solution, by mol, Ca
2+: V
5+=1-5: 1; More preferably, Ca
2+: V
5+=1-3: 1.
According to the present invention, in step 3) in, the mode of contact can be any way of contact well known in the art, for example can be that the solution behind the described silica removal and described soluble calcium salt are mixed, in order to obtain better mixed effect, preferably under agitation the solution behind the described silica removal is mixed with described soluble calcium salt; Under the preferable case, in order to be easy to solid-liquid separation after mixing, can also carry out standing sedimentation.Described contact conditions is not particularly limited, as long as it is just passable to make behind the silica removal vanadium in the solution transfer fully precipitation to; Consider the problem of vanadium transformation efficiency and production cycle, preferred, the solution behind the described silica removal and the duration of contact of soluble calcium salt are 1-10 hour; More preferably, be 1-5 hour described duration of contact, and most preferably, be 1-3 hour described duration of contact.
According to the present invention, in step 3) in, described soluble calcium salt can be the conventional various soluble calcium salts that can obtain with the vanadium reaction vanadic acid calcium that use in this area, for example, described soluble calcium salt can be calcium chloride and/or nitrocalcite; Be preferably calcium chloride.
Among the present invention, adopt the purity of EDTA titration measuring vanadic acid calcium product.
Below in conjunction with embodiment and Comparative Examples the method for preparing vanadic acid calcium by dephosphorization underflow slag of the present invention is further described, so that above object and advantages of the present invention are more obvious.
Embodiment 1
Get particle diameter at the dephosphorization underflow slag 500g of 75-125 micrometer range (main component: TV (total vanadium, below identical)/10.03 % by weight, the Si/5.06 % by weight, the P/0.602 % by weight, the Mn/4.61 % by weight, the Ca/8.83 % by weight), with 1000ml concentration be the NaOH aqueous solution of 60 % by weight, stirring also is heated to 60 ℃, behind the reaction 60min, filters, washs, obtain leach liquor 1512ml (TV:31.67g/L, Si:0.536g/L, P＜0.1g/L, V leaching rate 95.5%).
With leach liquor obtained above and 7.7g AlCl
3Mix, sedimentation was filtered after 3 hours, obtained supernatant liquor and with hydrochloric acid the pH value was adjusted to 10.5, with 103g CaCl
2Mix, stir after 5 hours and filter, 120 ℃ of lower oven dry solid phases, obtain 165.70g Ca
3(VO
4)
2, measuring its purity is 98.2%, vanadium recovery is 94.5 % by weight.
Vanadium recovery (%)=(in the vanadic acid calcium in the amount of vanadium (g)/dephosphorization underflow slag the amount (g) of total vanadium) * 100%, following method of calculation are identical.
Embodiment 2
Get particle diameter at the dephosphorization underflow slag 100g of 75-125 micrometer range (main component: TV/10.03%, Si/5.06%, P/0.602%, Mn/4.61%, Ca/8.83%), with 300ml concentration be the KOH aqueous solution of 40 % by weight, stir and be heated to 80 ℃, behind the reaction 120min, filter, wash, get leach liquor 324ml (TV:30.21g/L, Si:0.767g/L, P＜0.1g/L, V leaching rate 97.59%).
With leach liquor obtained above and 3.5g AlCl
3Mix, sedimentation was filtered after 4 hours, after the supernatant liquor that obtains is adjusted to 11 with hydrochloric acid pH value, with 42.6g CaCl
2Mix, stir after 2 hours and filter, the oven dry solid phase obtains 33.48g Ca
3(VO
4)
2, measuring its purity is 98.3%, vanadium recovery is 95.7 % by weight.
Embodiment 3
Get particle diameter in the dephosphorization underflow slag 200g of 75-125 micrometer range (main component: TV/10.03 % by weight, Si/5.06 % by weight, P/0.602 % by weight, the Mn/4.61 % by weight, the Ca/8.83 % by weight), with 1000ml concentration be the NaOH aqueous solution of 20% weight, stir and be heated to 100 ℃, behind the reaction 20min, filter, wash, get leach liquor 819ml (TV:23.43g/L, Si:0.653g/L, P＜0.1g/L, V leaching rate 95.66%).
With leach liquor obtained above and 15.3gAlCl
3Mix, sedimentation was filtered after 5 hours, obtained supernatant liquor and with hydrochloric acid the pH value was adjusted to 10.9, with 125.3g CaCl
2Mix, stir after 3 hours and filter, lower oven dry solid phase obtains 65.71gCa
3(VO
4)
2, measuring its purity is 98.2%, vanadium recovery is 93.7 % by weight.
Embodiment 4
Get particle diameter in the dephosphorization underflow slag 300g of 75-125 micrometer range (main component: TV/10.03 % by weight, Si/5.06 % by weight, P/0.602 % by weight, the Mn/4.61 % by weight, the Ca/8.83 % by weight), with 300ml concentration be the KOH aqueous solution of 80 % by weight, stir and be heated to 60 ℃, behind the reaction 60min, filter, wash, obtain leach liquor 329ml (TV:82.95g/L, Si:0.816g/L, P＜0.1g/L, V leaching rate 94.7%).
With leach liquor obtained above and 14.2g Mg (NO
3)
2Mix, sedimentation was filtered after 3 hours, obtained supernatant liquor and with hydrochloric acid the pH value was adjusted to 10.7, with 438.8g Ca (NO
3)
2Mix, stir after 1 hour and filter, the oven dry solid phase obtains 97.36gCa
3(VO
4)
2, measuring its purity is 98.6%, vanadium recovery is 93.0 % by weight.
By embodiment 1-4 as can be known, the dephosphorization underflow slag according to the present invention method of producing vanadic acid calcium has vanadium recovery height, the simple advantage of technical process.
Claims (12)
1. one kind prepares the method for vanadic acid calcium by dephosphorization underflow slag, and the method comprises the steps:
1) dephosphorization underflow slag is contacted with alkaline aqueous solution and carry out solid-liquid separation, obtain leach liquor;
2) with step 1) leach liquor that obtains contacts with desiliconizing agent and carries out silica removal, obtains the leach liquor behind the silica removal;
3) under alkaline condition, with step 2) leach liquor behind the silica removal that obtains contacts with soluble calcium salt, obtains vanadic acid calcium.
2. method according to claim 1, wherein, in step 1) in, take every gram dephosphorization underflow slag as benchmark, the feeding quantity of described alkaline aqueous solution is 1-10mL.
3. method according to claim 1 and 2, wherein, in step 1) in, the concentration of described alkaline aqueous solution is the 10-90 % by weight.
4. method according to claim 3, wherein, the alkaline matter in the described alkaline aqueous solution is sodium hydroxide and/or potassium hydroxide.
5. method according to claim 1, wherein, in step 1) in, the condition of described contact comprises that temperature is 30-200 ℃, the time is 20-400min.
6. method according to claim 1 and 2, wherein, in step 1) in, the particle diameter of described dephosphorization underflow slag is the 40-125 micron.
7. method according to claim 1, wherein, in step 2) in, described desiliconizing agent is selected from AlCl
3, FeCl
3And Mg (NO
3)
2In one or more.
8. according to claim 1 or 7 described methods, wherein, the add-on of described desiliconizing agent is, is as the criterion meter in molar ratio, the positively charged ion in the desiliconizing agent: Si with silicone content in the leach liquor
4+=1-10: 1.
9. method according to claim 1, wherein, in step 2) in, be 1-10 hour the duration of contact of described leach liquor and desiliconizing agent.
10. method according to claim 1, wherein, in step 3) in, the pH value of the leach liquor behind the described silica removal is 9-12.
11. method according to claim 1 is wherein, in step 3) in, the add-on of described soluble calcium salt is, is as the criterion with content of vanadium in the leach liquor behind the silica removal, by mol, Ca
2+: V
5+=1-5: 1.
12. according to claim 1 or 11 described methods, wherein, in step 3) in, described soluble calcium salt is calcium chloride and/or nitrocalcite.
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|---|---|---|---|
| CN2011102196836A CN102910674A (en) | 2011-08-02 | 2011-08-02 | Method for preparing calcium vanadate from phosphorus-removing underflow slag |
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|---|---|---|---|
| CN2011102196836A CN102910674A (en) | 2011-08-02 | 2011-08-02 | Method for preparing calcium vanadate from phosphorus-removing underflow slag |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182037A (en) * | 2007-11-23 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Method for recovering vanadium oxide from dephosphorization bottom flow slag |
| CN101724757A (en) * | 2009-12-31 | 2010-06-09 | 攀枝花新钢钒股份有限公司 | Method for preparing low-silicon and low-phosphorous vanadium liquid |
| CN102071321A (en) * | 2011-01-14 | 2011-05-25 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium and chromium from vanadium-containing steel slag by high-alkalinity potassium hydroxide |
-
2011
- 2011-08-02 CN CN2011102196836A patent/CN102910674A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182037A (en) * | 2007-11-23 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Method for recovering vanadium oxide from dephosphorization bottom flow slag |
| CN101724757A (en) * | 2009-12-31 | 2010-06-09 | 攀枝花新钢钒股份有限公司 | Method for preparing low-silicon and low-phosphorous vanadium liquid |
| CN102071321A (en) * | 2011-01-14 | 2011-05-25 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium and chromium from vanadium-containing steel slag by high-alkalinity potassium hydroxide |
Non-Patent Citations (1)
| Title |
|---|
| 杨守志: "《钒冶金》", 31 January 2010, 冶金工业出版社 * |
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Application publication date: 20130206 |