CN101285132A - Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale - Google Patents
Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale Download PDFInfo
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- CN101285132A CN101285132A CNA2008103020355A CN200810302035A CN101285132A CN 101285132 A CN101285132 A CN 101285132A CN A2008103020355 A CNA2008103020355 A CN A2008103020355A CN 200810302035 A CN200810302035 A CN 200810302035A CN 101285132 A CN101285132 A CN 101285132A
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Abstract
The invention provides a method for cleanly extracting vanadium from vanadium-containing carbonaceous shale, which comprises the steps of crushing the vanadium-containing carbonaceous shale, adding hydrochloric acid solution, heating, stirring, filtering, and preparing V from filtrate according to a conventional process2O5Adding fluorosilicic acid solution into filter residue, heating, gradually adding oxidant, stirring, filtering, and making filtrate into V2O5The vanadium-containing ore in the invention does not need to be roasted, the pollution of the vanadium extraction process to the atmospheric environment is eliminated, hydrochloric acid and fluosilicic acid are adopted as main leaching agents, no new precipitate is generated, and vanadium in the vanadium-containing carbonaceous shale is selectively leached, so that the agent dosage is reduced, and the vanadium extraction cost is reduced; the invention has the advantages of mild vanadium extraction conditions, high vanadium leaching rate, low energy consumption, low equipment requirement, high production safety and investment and operation cost saving.
Description
Technical field
The present invention relates to vanadium extraction technical field from contain navajoite stone, particularly relate to the method for cleaning vanadium extraction from contain the vanadium carbonaceous shale.
Background technology
Vanadium is the important raw and processed materials of high-tech industries such as preparation special steel, V-Ti, catalyzer and vanadium fluid flow energy storage cell, is widely used in the The modern industry technology.The navajoite resource mainly contains vanadium titano-magnetite and contains the vanadium carbonaceous shale, and contain the vanadium carbonaceous shale and account for 87% of China's vanadium total reserves, be the valuable source of vanadium.The navajoite stock number that Guizhou Province has controlled surpasses 600,000 tons, and prospective reserves is more than 1,000,000 tons, and association has valuable constituents such as nickel, molybdenum mostly, is Guizhou Province's potential advantage Mineral resources.
To the process for extracting research that contains vanadium in the vanadium carbonaceous shale at most, the most sophisticated technology remains sodium roasting technology.The greatest problem one that sodium roasting technology exists is that environmental pollution is very serious, the 2nd, and the rate of recovery is very low, generally only is the 40～50%, the 3rd, can not comprehensively reclaim the valuable element of association in the ore, halts at present comprehensively.
At present, contain vanadium carbonaceous shale environment-friendly type process for extracting vanadium and mainly contain that calcification baking is acid-leaching vanadium-extracted, saltless roasting is acid-leaching vanadium-extracted, directly leach several types such as vanadium extraction.Directly leaching process for extracting vanadium mainly is divided into directly acid-leaching vanadium-extracted, oxygen and presses the several types such as acid-leaching vanadium-extracted and alkaline pressure of oxygen leaching vanadium extraction.Directly leaching vanadium extraction and not only save roasting workshop section, and eliminated and contain the influence of vanadium carbonaceous shale vanadium extraction process to air ambient, is very rising process for extracting vanadium.
Directly acid-leaching vanadium-extracted requirement to ore properties is especially high, is only applicable to the very high ore of only a few degree of oxidation.Directly acidleach and oxygen press acidleach generally to adopt sulfuric acid as the main medicament that leaches, sulfuric acid easily and the reaction of the calcium in the ore generate by products such as gypsum, hinder and leach medicament further and a year vanadium minerals effect, influence the leaching yield of vanadium.It is 150～180 ℃ that oxygen presses process for extracting vanadium by acid leaching to extract temperature, and pressure is more than 0.5MPa, and the sulfuric acid consumption is 25～30% of an ore amount, has the energy consumption height, and the acid consumption is high, to the equipment requirements height, and weak point such as security is low.Oxygen presses the alkali soaking technology to be actually to carry from bayer's process that aluminium technology dislocation comes, and the problem of existence and oxygen press acidleach similar, and the subsequent disposal difficulty is bigger, generally only is used for bayer's process and carries when aluminium technology is comprehensive to reclaim vanadium and using.
Summary of the invention
Technical problem to be solved by this invention be overcome existing vanadium extraction technology to the pollution of environment, improve vanadium the leaching yield and the rate of recovery, reduce production costs, a kind of method of cleaning vanadium extraction from contain the vanadium carbonaceous shale is provided.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
The method of cleaning vanadium extraction from contain the vanadium carbonaceous shale provided by the invention: will contain the vanadium carbonaceous shale and pulverize, adding concentration is 5～22% hydrochloric acid solution, and heating is stirred, and filters, and filtrate routinely technology is produced V
2O
5, adding concentration is 5～25% silicate fluoride solution in the filter residue, and heating progressively adds oxidant, stirs, and filters, and filtrate routinely technology is produced V
2O
5
The present invention also limits the consumption of various medicaments in the method for above-mentioned cleaning vanadium extraction from contain the vanadium carbonaceous shale: will contain the vanadium carbonaceous shale and pulverize, the concentration that adds ore amount 50～200% (weight) is 10～20% hydrochloric acid solution, heating, stir, filter, filtrate routinely technology is produced V
2O
5, the concentration that adds ore amount 50～200% (weight) in the filter residue is 10～20% silicate fluoride solution, heats, and progressively adds the oxidant of ore amount 1～10% (weight), stirs, and filters, filtrate routinely technology is produced V
2O
5
Particularly, the method of aforementioned cleaning vanadium extraction from contain the vanadium carbonaceous shale: will contain the fragmentation of vanadium carbonaceous shale, ore grinding to granularity and account for 60～90% (weight) of whole ores for the ore particle of-0.15mm, the concentration that adds ore amount 50～150% (weight) is 10～20% hydrochloric acid solution, be heated to 60～100 ℃, stir, leached 1～5 hour, and filtered, filtrate routinely technology is produced V
2O
5, the concentration that adds ore amount 50～150% (weight) in the filter residue is 10～20% silicate fluoride solution, is heated to 60～100 ℃, the oxidant that progressively adds ore amount 1～5% (weight) stirs, and leaches 2～8 hours, filter, filtrate routinely technology is produced V
2O
5
The process conditions that the present invention is preferably as follows are carried out vanadium extraction: will contain the fragmentation of vanadium carbonaceous shale, ore grinding to granularity and account for 75% (weight) of whole ores for the ore particle of-0.15mm, the concentration that adds ore amount 75% (weight) is 20% hydrochloric acid solution, be heated to 80 ℃, stir, leached 2 hours, filter, filtrate routinely technology is produced V
2O
5, the concentration that adds ore amount 80% (weight) in the filter residue is 15% silicate fluoride solution, is heated to 75 ℃, progressively adds the oxidant of ore amount 5% (weight), stirs, and leaches 6 hours, filters, filtrate routinely technology is produced V
2O
5
The used preferred sodium chlorate of oxygenant in the method for aforementioned cleaning vanadium extraction from contain the vanadium carbonaceous shale.
Key of the present invention is how to adopt technology free from environmental pollution that vanadium in the ore is transferred in the infusion solution, the contriver is in research process, find to adopt the leaching yield of direct oxidation acid leaching process not high, many technical parameters have been adjusted, leaching yield also only reaches about 46%, and the oxygenant consumption is too high, and is also uneconomical from cost.The vanadium that contains in the vanadium carbonaceous shale mainly is to exist with trivalent vanadium, and water insoluble, non-oxidizable diluted acid of trivalent vanadium and diluted alkaline are mainly with the Al on the isomorphous form replacement roscoelite class silicate mineral lattice
3+, roscoelite class silicate mineralogical property is very stable, is difficult for destroyed and the release vanadium ion, and therefore, the key that improves the vanadium leaching yield is: the one, creating conditions to discharge vanadium from lattice silicate; The 2nd, make trivalent vanadium be oxidized to water miscible tetravalence vanadium or pentavalent vanadium.
By top analysis, chemical property in conjunction with vanadium, the contriver think available technology adopting sulfuric acid as the main defective that leaches the solvent maximum be sulfuric acid easily and the by products such as calcium sulfate of the calcium water generation reaction dissolubility difference in the ore, hinder sulfuric acid further and carry a vanadium minerals effect, therefore just consider employing and effect back generation CaCl such as calcium, magnesium, iron
2, MgCl
2, FeCl
2Etc. the material of good water solubility the leaching medicament---hydrochloric acid is as the main leaching solvent of fs; In the tailings of having removed impurity such as calcium, magnesium, iron, except that roscoelite class silicate minerals, also there is a large amount of SiO simultaneously
2Composition, so the contriver considers to adopt and can be optionally carries the medicament H of vanadium minerals effect with roscoelite etc.
2SiF
6As the main leaching medicament of subordinate phase, the structure of selective destruction roscoelite makes vanadium be able to discharge from the roscoelite lattice, thereby reaches the purpose that selectivity leaches vanadium.
The present invention cleans the main chemical reactions that takes place in the extraction vanadium method:
Fs:
2HCl+CaCO
3＝CaCl
2+H
2O+CO
2↑
2HCl+MgCO
3＝MgCl
2+H
2O+CO
2↑
6HCl+Fe
2O
3＝2FeCl
3+3H
2O
VO
2+4HCl＝VCl
4+2H
2O
V
2O
5+10HCl＝2VCl
5+5H
2O
Subordinate phase:
3V
2O
3SiO
2Al
2O
3(roscoelite class silicate mineral)+3H
2SiF
6+ 18HCl+NaClO
3=6AlF
3+ 6SiO
2+ 6VCl
4+ NaCl+3H
2O
Compared with prior art, the navajoite stone that contains among the present invention need not roasting, has eliminated the pollution of process for extracting vanadium to atmospheric environment; According to containing main character of carrying vanadium minerals in the vanadium carbonaceous shale, adopt hydrochloric acid and silicofluoric acid as the main medicament that leaches, calcium in hydrochloric acid and the ore, the extraordinary materials of impurity water generation reaction dissolubility such as magnesium, do not generate new throw out, thereby do not influence the leaching yield of vanadium, a silicofluoric acid and a year vanadium minerals effect, change the structure of carrying vanadium minerals, make trivalent vanadium ion break away from the constraint of the lattice point of silicate, be oxidized to tetravalence soluble in water or pentavalent vanadium ion and enter solution under the effect of oxygenant, selectivity leaches vanadium wherein, has reduced the effect of medicament and other mineral, reduce dosing, reduced the vanadium extraction cost; Be oxidized to soluble in water water insoluble in the ore and trivalent vanadium diluted acid and tetravalence vanadium or pentavalent vanadium diluted acid by wet oxidation, thereby realize the purpose of cleaning vanadium extraction.And the present invention carries out under normal pressure, extraction temperature is generally at 80～100 ℃, the leaching yield of vanadium can reach more than 90%, the vanadium extraction mild condition, the leaching yield height of vanadium, energy consumption are only pressed 1/2nd to 1/3rd of acid leaching process for oxygen, and equipment requirements is low, the production security height is reduced investment outlay and working cost.
Embodiment
Embodiment 1, get and contain 100 kilograms of vanadium carbonaceous shales, broken, ore grinding to granularity accounts for 75% of whole ores for the ore particle of-0.15mm, add 100 kilograms of concentration and be 15% hydrochloric acid solution, be heated to 80 ℃, stir, leached 2 hours, and filtered, filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
580 kilograms of concentration of adding are 15% silicate fluoride solution in the filter residue, are heated to 75 ℃, progressively add 5 kilograms sodium chlorate, stir, and leach 6 hours, filter, and filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5
Embodiment 2, get and contain 100 kilograms of vanadium carbonaceous shales, broken, ore grinding to granularity accounts for 60～70% of whole ores for the ore particle of-0.15mm, add 50 kilograms of concentration and be 22% hydrochloric acid solution, be heated to 60 ℃, stir, leached 5 hours, and filtered, filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5150 kilograms of concentration of adding are 10% silicate fluoride solution in the filter residue, are heated to 100 ℃, progressively add 1 kilogram of sodium chlorate, stir, and leach 2 hours, filter, and filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5
Embodiment 3, get and contain 100 kilograms of vanadium carbonaceous shales, broken, ore grinding to granularity accounts for 90% of whole ores for the ore particle of-0.15mm, add 200 kilograms of concentration and be 5% hydrochloric acid solution, be heated to 100 ℃, stir, leached 1 hour, and filtered, filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
560 kilograms of concentration of adding are 25% silicate fluoride solution in the filter residue, are heated to 60 ℃, progressively add 8 kilograms of sodium chlorate, stir, and leach 8 hours, filter, and filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5
Embodiment 4, get and contain 100 kilograms of vanadium carbonaceous shales, broken, ore grinding to granularity accounts for 80% of whole ores for the ore particle of-0.15mm, add 70 kilograms of concentration and be 10% hydrochloric acid solution, be heated to 80 ℃, stir, leached 4 hours, and filtered, filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5100 kilograms of concentration of adding are 12% silicate fluoride solution in the filter residue, are heated to 70 ℃, progressively add 10 kilograms of sodium chlorate, stir, and leach 8 hours, filter, and filtrate is extracted V through operations such as purification, extraction, reextraction, ammonium salt precipitations
2O
5
Claims (5)
1. clean the method for vanadium extraction from contain the vanadium carbonaceous shale, it is characterized in that: will contain the vanadium carbonaceous shale and pulverize, adding concentration is 5～22% hydrochloric acid solution, heating, stir, filter, filtrate routinely technology is produced V2O5, adding concentration is 5～25% silicate fluoride solution in the filter residue, heating progressively adds oxidant, stirs, filter, filtrate routinely technology is produced V2O5.
2. according to the described method that from contain the vanadium carbonaceous shale, cleans vanadium extraction of claim 1, it is characterized in that: will contain the vanadium carbonaceous shale and pulverize, the concentration that adds ore amount 50～200% (weight) is 10～20% hydrochloric acid soln, heating, stir, filter, filtrate technology is routinely produced V2O5, the concentration that adds ore amount 50～200% (weight) in the filter residue is 10～20% silicate fluoride solution, heat, progressively add the oxygenant of ore amount 1～10% (weight), stir, filter, filtrate technology is routinely produced V2O5.
3. according to the described method that from contain the vanadium carbonaceous shale, cleans vanadium extraction of claim 2, it is characterized in that: will contain the fragmentation of vanadium carbonaceous shale, ore grinding to granularity accounts for 60～90% (weight) of whole ores for the ore particle of-0.15mm, the concentration that adds ore amount 50～150% (weight) is 10～20% hydrochloric acid soln, be heated to 60～100 ℃, stir, leached 1～5 hour, filter, filtrate technology is routinely produced V2O5, the concentration that adds ore amount 50～150% (weight) in the filter residue is 10～20% silicate fluoride solution, be heated to 60～100 ℃, the oxygenant that progressively adds ore amount 1～5% (weight) stirs, and leaches 2～8 hours, filter, filtrate technology is routinely produced V2O5.
4. according to the described method that from contain the vanadium carbonaceous shale, cleans vanadium extraction of claim 3, it is characterized in that: will contain the fragmentation of vanadium carbonaceous shale, ore grinding to granularity accounts for 75% (weight) of whole ores for the ore particle of-0.15mm, the concentration that adds ore amount 75% (weight) is 20% hydrochloric acid soln, be heated to 80 ℃, stir, leached 2 hours, filter, filtrate technology is routinely produced V2O5, and the concentration that adds ore amount 80% (weight) in the filter residue is 15% silicate fluoride solution, be heated to 75 ℃, the oxygenant that progressively adds ore amount 5% (weight) stirs, and leaches 6 hours, filter, filtrate technology is routinely produced V2O5.
5. according to the method for the described cleaning vanadium extraction from contain the vanadium carbonaceous shale of claim 1-4, it is characterized in that: described oxygenant is a sodium chlorate.
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| CN200810302035A CN100587089C (en) | 2008-06-05 | 2008-06-05 | Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale |
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| CN200810302035A CN100587089C (en) | 2008-06-05 | 2008-06-05 | Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale |
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| CN101285132A true CN101285132A (en) | 2008-10-15 |
| CN100587089C CN100587089C (en) | 2010-02-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220487A (en) * | 2011-06-02 | 2011-10-19 | 上海格泰实业发展有限公司 | Method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore |
| RU2739044C1 (en) * | 2020-03-11 | 2020-12-21 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method for complex processing of carbonaceous raw material containing non-ferrous metals |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1023693C (en) * | 1990-07-12 | 1994-02-09 | 江西省煤炭工业科学研究所 | Process for extracting of vanadium pentoxide by water immersion from cured mixture of stone coal ash with surfuric acid by heating |
| CN1059762A (en) * | 1991-07-18 | 1992-03-25 | 丁中南 | The novel process of V 2 O 5 production by chloric acid chlorination method |
| US5494648A (en) * | 1994-01-31 | 1996-02-27 | The United States Of America As Represented By The Secretary Of The Interior | Process for removing thorium and recovering vanadium from titanium chlorinator waste |
-
2008
- 2008-06-05 CN CN200810302035A patent/CN100587089C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220487A (en) * | 2011-06-02 | 2011-10-19 | 上海格泰实业发展有限公司 | Method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore |
| CN102220487B (en) * | 2011-06-02 | 2012-12-19 | 上海格泰实业发展有限公司 | Method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore |
| RU2739044C1 (en) * | 2020-03-11 | 2020-12-21 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method for complex processing of carbonaceous raw material containing non-ferrous metals |
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| CN100587089C (en) | 2010-02-03 |
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