CN102220487B - Method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore - Google Patents
Method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore Download PDFInfo
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- CN102220487B CN102220487B CN2011101471944A CN201110147194A CN102220487B CN 102220487 B CN102220487 B CN 102220487B CN 2011101471944 A CN2011101471944 A CN 2011101471944A CN 201110147194 A CN201110147194 A CN 201110147194A CN 102220487 B CN102220487 B CN 102220487B
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- vanadium
- clay
- aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for extracting vanadium and aluminum from vanadium-containing stone coal and clay vanadium ore, which belongs to the technical field of extraction of rare metals. A vanadium source is reacted with a leaching agent comprising silicofluoric acid and water for getting a solution containing the vanadium and the aluminum, vanadic oxide is further obtained through the ion exchange method or the solvent extraction method, and aluminum salts are finally recovered from the solution after vanadium extraction. By adopting the method, hydrofluosilic acid can be recycled for a plurality of times and the environmental pollution is reduced; and the problem that a by-product, namely tschermigite with limited purposes is generated in the prior art can be further solved, and iron-free aluminum sulfate which can be used for paper-making is generated through the solvent extraction method.
Description
Technical field
What the present invention relates to is the method in a kind of rare metal extractive technique field, specifically is a kind of method of from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium.
Background technology
Vanadium is a kind of important rare metal, is widely used for catalyzer of producing steel alloy, non-ferrous metal alloy and chemical industry etc.China extensively distributes contains the scherbinaite coal and the clay navajoite is important vanadium extraction raw material.Also contain valuable metals such as aluminium in this type mineral.
The technology of from this type navajoite, extracting vanadium at present is divided into two types: one type is to select for use pyrometallurgy to handle, promptly add different salt with containing the vanadium raw materials roasting, is divided into oxidizing roasting, sodiumizing-oxidizing roasting, calcification baking, sodium calcification baking again.Roasting material water or dilute sulphuric acid are leached, make vanadium and other element get into solution.Another kind ofly directly use high density, heavy dose of sulfuric acid in high temperature (greater than 95 degrees centigrade) long-time (about 10 to 30 hours) leaching for containing vanadium raw materials; Perhaps add other additive or claim promotor with sulfuric acid; For example Calcium Fluoride (Fluorspan), Sodium Fluoride, silicofluoric acid, ydrogen peroxide 50, hypochlorite etc.; Under normal temperature and/or high temperature, leach with different solid-liquid ratios.After changing vanadium over to solution, available existing method: IX or solvent extration obtain to meet the Vanadium Pentoxide in FLAKES more than 98 grades among the GB3283-87 from contain vanadium solution.
Produce a large amount of toxic and harmfuls during the roasting of first kind technology, environmental pollution is serious, complex process, and the recovery of vanadium low (50%-60%).Second type of technology extraction time is long, and energy consumption is high, and acid consumption is big, and cost is very high, and the leaching rate of vanadium is the highest to be had only about 80%.And this technology is very low to the solubility rate that contains the costly like this metal of aluminium in scherbinaite coal and the clay navajoite, and the value of comprehensive utilization is also low.Up to now, it is good still to lack a kind of metal recovery rate height, environmental friendliness, comprehensive utilization of resources, the method for from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium that adaptability to raw material is wide.
Further retrieval is found; Chinese patent document number CN 101624649A; Open day on January 13rd, 2010, to have put down in writing and a kind ofly from contain the scherbinaite colliery, has leached the method for vanadium with the collaborative sulfuric acid of silicofluoric acid, this technology will contain the fragmentation of scherbinaite colliery, wet grinding to granularity less than 0.15mm; Water is 1-3 with the volume mass ratio that contains the scherbinaite colliery in the ore pulp that ore grinding obtains: 1; Add silicofluoric acid and sulfuric acid and carry out the leaching of vanadium, the silicofluoric acid consumption is calculated as the 5%-15% that contains scherbinaite colliery quality with the silicofluoric acid of 100% mass concentration, and the sulfuric acid consumption is the 10%-25% that contains scherbinaite colliery quality; 80 ℃-95 ℃ of leaching process temperature. extraction time 2h-20h, leach after liquid-solid separation obtains containing vanadium leachate.Leach liquor is used the iron powder reducing ferric ion, with lime and ammoniacal liquor the pH value is adjusted to 2.8-3.0 after, through SX, oxidation, adding ammoniacal liquor, obtain ammonium poly-vanadate deposition, ammonium poly-vanadate is through calcining preparation powdery Vanadium Pentoxide in FLAKES product.Leach for a long time but must expend sulfuric acid high temperature during this technology implementation, and complex technical process, energy consumption is high, and except that vanadium, other valuable metals can not efficient recovery.The colloidal sol shape material that contains impurity such as iron and a large amount of silicon and aluminium in the leach liquor makes that subsequent treatment process such as solid-liquid separation is very difficult, and the difficulty of liquid waste disposal and cost are all very high.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists, a kind of method of from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium is provided, from contain scherbinaite coal and clay navajoite, extract vanadium and aluminium.
The present invention realizes through following technical scheme; The present invention obtains containing the solution of vanadium and aluminium through the leaching agent reaction that vanadium source and silicofluoric acid and water are formed; And further obtain Vanadium Pentoxide in FLAKES through ion exchange method, after vanadium extraction, reclaim iron-free aluminium salt with solvent extration the liquid at last.
Concrete technical process of the present invention is: at first in leach liquor, add oxygenants such as VAL-DROP or Youxiaolin or potassium permanganate the low price vanadium is oxidized to pentavalent, with lime powder pH value of solution is transferred to 2.0-2.5 again, with liquid before the calcium slag filtration acquisition exchange.With the vanadium in the liquid before the D301 ion exchange resin absorption exchange, and aluminium is stayed in the liquid of exchange back.With the rich resin that carries vanadium of the sodium hydroxide solution wash-out of 1mol/L-3mol/L, obtaining concentration is the V of 40-120g/L
2O
5Rich vanadium solution.In rich vanadium solution, add ammonium chloride, obtain ammonium meta-vanadate.Ammonium meta-vanadate is 500～550 ℃ of following calcinations, produces the powdery Vanadium Pentoxide in FLAKES that quality is superior among the GB3283-87 98 grades.
In the liquid of exchange back, add Sodium sulfate anhydrous.min(99) (Na while stirring
2SO
4), obtain sodium silicofluoride and Sodium Fluoride mixture.Add lime powder in the solution after separating fluorochemical, pH is transferred to 6.5-7.0 aluminium is got in the slag.After the solid-liquid separation, obtain the aluminium slag.With an amount of sulfuric acid to leach aluminium slag, obtain alum liquor.With the iron in the solvent extration extraction alum liquor, the extraction agent component is (V/V): N235:20%; TBP:10%; No. 260 solvent oils: 70%.Alum liquor after the deironing is heated to 118 ℃ of boiling points, and crystallisation by cooling obtains non-iron aluminium sulfate, and it is one of raw material of papermaking.
The mixture of Sodium Silicofluoride 98min and Sodium Fluoride is put into reaction vessels, add the vitriol oil, 250-350 ℃ of reaction down, produce hydrogen fluoride gas, water absorbs hydrogen fluoride gas, obtains hydrofluoric acid.In hydrofluoric acid, add silica powder, stirred at normal temperatures 1-5 hour, obtain silicofluoric acid.The silicofluoric acid that obtains is used for leaching raw ore again.So move in circles.
Described vanadium source is: fineness is the ashes after 60 order to 170 purpose powderies contain scherbinaite coal, clay navajoite or contain the fluidized bed burning of scherbinaite, and wherein: the component and the mass percent (%) that contain the scherbinaite coal are SiO
2: 52.76; Fe:3.01; Al
2O
3: 13.72; CaO:0.83; V
2O
5: 1.28; The component of clay navajoite and mass percent (%) are SiO
2: 69.76; Fe:2.16; Al
2O
3: 17.1; CaO:0.93; V
2O
5: 1.27; The component and the mass percent (%) that contain the ashes after the fluidized bed burning of scherbinaite are SiO
2: 63.41; Fe
2O
3: 4.83; Al
2O
3: 20.35; CaO:0.40; V
2O
5: 1.36.
The ratio of water and industrial silicofluoric acid is (v/v) in the described leaching agent: 10: 13～15.
Silicofluoric acid concentration is 3-40% (weight percent concentration) in the described leaching agent.
Described reaction is meant: reaction is 15 minutes-200 minutes under 70 ℃ of-130 ℃ of environment.
Described aluminium salt is: ALUMNIUM FLUORIDE, Tai-Ace S 150 or white lake.
Compared with prior art, the reaction times of the present invention is short, and energy consumption is lower, and solid-liquid separation and subsequent disposal are easy, can silicofluoric acid repeatedly be recycled, and have reduced environmental pollution widely; When extracting Vanadium Pentoxide in FLAKES, the present invention has further solved the very little sub product tschermigite of market capacity that produces in the prior art, produce market capacity big, can be as the non-iron aluminium sulfate of paper making raw material.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1:
Contain scherbinaite coal 100g, granularity-170 order adds entry 100mL, and industrial silicofluoric acid 130mL at 95 ℃ of following reaction 2h, filters and with tap water drip washing three times, acquisition leach liquor 309.6mL, and leached mud 89.5g, leach liquor contains V
2O
53.90g/L, Al
2O
331.06g/L leached mud contains V
2O
50.068%, Al
2O
34.12%.In leach liquor, add Sodium sulfate anhydrous.min(99) (Na
2SO
4) 32g, obtain Sodium Silicofluoride 98min 41.2g, in the later solution of separate fluorine water glass, add NaClO
30.4g, lime powder 14g, pH value of solution 2.20 with D301 resin 7mL absorption vanadium, with the rich resin that carries of 8% sodium hydroxide solution washing, produces V
2O
5Concentration is the elutriant 27.1mL of 43.6g/L, in elutriant, adds industrial ammonium chloride 2.5g, obtains ammonium meta-vanadate, and ammonium meta-vanadate at 530 ℃ of following calcination 3h, is obtained powdery V
2O
51.09g, its V
2O
5Content is 99.1%.Sodium Silicofluoride 98min is put into reactor drum, add the vitriol oil (98%) 12mL, react 1.5h down at 310 ℃, the silicofluoric acid gas that the water absorption reaction produces obtains silicate fluoride solution 100.5mL, and silicofluoric acid concentration is 28.2%.
In the liquid of absorption back, add lime powder (CaO) 5.6 grams, control solution endpoint pH is 6.6, and the aluminium slag promptly precipitates.Aluminium slag after filtering with tap water drip washing three times, is added the 150mL tap water again and sizes mixing, add vitriol oil 16mL while stirring,, obtain Aluminum Sulfate Solution solution 220mL with the slag elimination and with the clear water washing.(it consists of (V/V): N23520% with extraction agent; TBP 10%; No. 260 solvent oils 70%) iron in the four-stage counter-current extraction Aluminum Sulfate Solution solution.Alum liquor after the deironing is concentrated into 118 ℃ of boiling points, and crystallisation by cooling gets non-iron aluminium sulfate 54.2 gram, wherein Al
2O
3Content is 16.01%, and iron level is 0.004%.
Embodiment 2:
Clay navajoite 100g, granularity-60 order adds entry 90mL, and industrial silicofluoric acid 140mL at 98 ℃ of following reaction 2h, filters and with tap water drip washing three times, acquisition leach liquor 303.2mL, leached mud 88g, leach liquor contains V
2O
53.80g/L, Al
2O
336.98g/L leached mud contains V
2O
50.12%, Al
2O
35.83%.In leach liquor, add Sodium sulfate anhydrous.min(99) (Na
2SO
4) 34.5g, obtain Sodium Silicofluoride 98min 43.2g, in the later solution of separate fluorine water glass, add NaClO
30.4g, lime powder 13g, pH value of solution 2.15 with D301 resin 7mL absorption vanadium, with the rich resin that carries of 8% sodium hydroxide solution washing, produces V
2O
5Concentration is the elutriant 25.4mL of 40.2g/L, in elutriant, adds industrial ammonium chloride 2.4g, obtains ammonium meta-vanadate, and ammonium meta-vanadate at 530 ℃ of following calcination 3h, is obtained powdery V
2O
51.09g, its V
2O
5Content is 98.7%.Sodium Silicofluoride 98min is put into reactor drum, add the vitriol oil (98%) 13mL, react 1h down at 305 ℃, the silicofluoric acid gas that the water absorption reaction produces obtains silicate fluoride solution 110.7mL, and silicofluoric acid concentration is 26.9%.
In the liquid of absorption back, add lime powder (CaO) 6.2 grams, control solution endpoint pH is 6.5, and the aluminium slag promptly precipitates.Aluminium slag after filtering with tap water drip washing three times, is added the 160mL tap water again and sizes mixing, add vitriol oil 17mL while stirring,, obtain Aluminum Sulfate Solution solution 240mL with the slag elimination and with the clear water washing.(it consists of (V/V): N23520% with extraction agent; TBP 10%; No. 260 solvent oils 70%) iron in the four-stage counter-current extraction Aluminum Sulfate Solution solution.Alum liquor after the deironing is concentrated into 117 ℃ of boiling points, and crystallisation by cooling gets non-iron aluminium sulfate 65.7. gram, wherein Al
2O
3Content is 16.12%, and iron level is 0.004%.
Embodiment 3:
Contain the lime-ash 100g after the fluidized bed burning of scherbinaite, granularity-120 order adds entry 100mL, and industrial silicofluoric acid 150mL, filters and with tap water drip washing three times acquisition leach liquor 324.5mL, leached mud 86g at 96 ℃ of reaction 2h down.Leach liquor contains V
2O
54.01g/L, Al
2O
345.2g/L leached mud contains V
2O
50.063%, Al
2O
36.43%.In leach liquor, add Sodium sulfate anhydrous.min(99) (Na
2SO
4) 37g, obtain Sodium Silicofluoride 98min 46.8g, in the later solution of separate fluorine water glass, add NaClO
30.4g, lime powder 15g, pH value of solution 2.30 with D301 resin 7mL absorption vanadium, with the rich resin that carries of 8% sodium hydroxide solution washing, produces V
2O
5Concentration is the elutriant 27.3mL of 44.3g/L, in elutriant, adds industrial ammonium chloride 2.6g, obtains ammonium meta-vanadate, and ammonium meta-vanadate at 530 ℃ of following calcination 3h, is obtained powdery V
2O
51.19g, its V
2O
5Content is 99.10%.Sodium Silicofluoride 98min is put into reactor drum, add the vitriol oil (98%) 15mL, react 1.5h down at 310 ℃, the silicofluoric acid gas that the water absorption reaction produces obtains silicate fluoride solution 120.8mL, and silicofluoric acid concentration is 27.9%.
In the liquid of absorption back, add lime powder (CaO) 8.4 grams, control solution endpoint pH is 6.7, and the aluminium slag promptly precipitates.Aluminium slag after filtering with tap water drip washing three times, is added the 190mL tap water again and sizes mixing, add vitriol oil 23mL while stirring,, obtain Aluminum Sulfate Solution solution 320mL with the slag elimination and with the clear water washing.(it consists of (V/V): N23520% with extraction agent; TBP 10%; No. 260 solvent oils 70%) iron in the four-stage counter-current extraction Aluminum Sulfate Solution solution.Alum liquor after the deironing is concentrated into 119 ℃ of boiling points, and crystallisation by cooling gets non-iron aluminium sulfate 78.30 gram, wherein Al
2O
3Content is 16.82%, and iron level is 0.003%.
Claims (4)
1. method of from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium; It is characterized in that; Leaching agent reaction through vanadium source and silicofluoric acid and water are formed obtains containing vanadium and aluminum solutions; And further obtain Vanadium Pentoxide in FLAKES through IX or solvent extration, after vanadium extraction, reclaim aluminium salt at last the liquid;
Described vanadium source is: fineness is the ashes after 60 order to 170 purpose powdered contain scherbinaite coal, clay navajoite or contain the fluidized bed burning of scherbinaite.
2. the method for from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium according to claim 1 is characterized in that the volume ratio of water and industrial silicofluoric acid is 10:13～15 in the described leaching agent.
3. the method for from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium according to claim 2 is characterized in that described silicofluoric acid concentration is 3-40%.
4. the method for from contain scherbinaite coal and clay navajoite, extracting vanadium and aluminium according to claim 1 is characterized in that described reaction is meant: reaction is 15 minutes-200 minutes under 70 ℃ of-130 ℃ of environment.
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| CN102560104A (en) * | 2012-02-07 | 2012-07-11 | 九江佰盾钒技术贸易有限公司 | Method for increasing leaching rate of vanadium from stone coal vanadium ores |
| CN107983764B (en) * | 2017-12-19 | 2022-09-06 | 湖南华麒资源环境科技发展有限公司 | Method for repairing and improving quality of chromium-polluted soil |
| CN115198116A (en) * | 2022-07-21 | 2022-10-18 | 上海寰泰绿钒科技有限公司 | Method for extracting vanadium from vanadium-containing stone coal |
| CN116516180B (en) * | 2023-07-04 | 2023-09-22 | 北京科技大学 | Method for extracting vanadium by high-efficiency direct leaching of stone coal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285132A (en) * | 2008-06-05 | 2008-10-15 | 贵州省地质矿产中心实验室 | Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale |
| CN101624649A (en) * | 2009-08-04 | 2010-01-13 | 长沙达华矿业技术开发有限公司 | Method for leaching vanadium from vanadous stone coal ore with fluosilicic acid and sulphuric acid |
| CN102010984A (en) * | 2010-12-23 | 2011-04-13 | 中南大学 | Method for extracting vanadium in coal gangue |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285132A (en) * | 2008-06-05 | 2008-10-15 | 贵州省地质矿产中心实验室 | Method for cleanly extracting vanadium from vanadium-containing carbonaceous shale |
| CN101624649A (en) * | 2009-08-04 | 2010-01-13 | 长沙达华矿业技术开发有限公司 | Method for leaching vanadium from vanadous stone coal ore with fluosilicic acid and sulphuric acid |
| CN102010984A (en) * | 2010-12-23 | 2011-04-13 | 中南大学 | Method for extracting vanadium in coal gangue |
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