CN102274795B - Beneficiation method for enriching vanadium pentoxide from high calcium type vanadium ore - Google Patents
Beneficiation method for enriching vanadium pentoxide from high calcium type vanadium ore Download PDFInfo
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- CN102274795B CN102274795B CN201110191549XA CN201110191549A CN102274795B CN 102274795 B CN102274795 B CN 102274795B CN 201110191549X A CN201110191549X A CN 201110191549XA CN 201110191549 A CN201110191549 A CN 201110191549A CN 102274795 B CN102274795 B CN 102274795B
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Abstract
The invention discloses a beneficiation method for enriching vanadium pentoxide from high calcium type vanadium ore. The method comprises the following steps of: crushing the raw ore of the high calcium type vanadium ore; ball milling the vanadium ore till a certain particle size is reached and then taking the vanadium ore as feedstock in floatation operation; adding a pH modifier, a vanadium ore containing inhibitor and a calcium mineral collector to obtain floatation pulp; performing floatation of the calcium mineral to obtain calcium concentrate; taking floatation bottom flow as vanadium concentrate; and taking the vanadium concentrate as the raw material for smelting and extracting vanadium. According to the method disclosed by the invention, by utilizing a beneficiation technology with low cost, most of calcium mineral in the raw vanadium ore can be removed; the level for smelting and extracting the vanadium raw material is effectively increased; the acid consumption for smelting and extracting the vanadium is reduced; and therefore, purposes of compressing the handling capacity for smelting materials, reducing the smelting investment and reducing unit product production cost are achieved.
Description
Technical field
The present invention relates to grinding process and floatation process, be specially from the beneficiation method of high-calcium type navajoite enrichment vanadic anhydride.
Background technology
A kind of high-calcium type navajoite, mineral composition is that illite (hydromuscovite), sericite, dolomite (and iron content mangandolomite), calcite (and contain calcimangite, ferroan calcite), quartz, opal, kaolinite, chlorite, feldspar, limonite (goethite), bloodstone, tourmaline, hornblend, garnet, the tremolite etc., contain a small amount of sulfide, apatite and carbonaceous thing etc.
Xingshan County gingko garden, Hubei Province silver navajoite belongs to the high-calcium type navajoite, and the raw ore pentoxide content is 0.96%, and in ore, callable valuable component is mainly vanadic anhydride.Essential mineral consists of illite, sericite, dolomite, calcite, quartz, opal and limonite etc.Vanadium is mainly with Low Valent Vanadium (V
3+, V
4+) form exist, account for more than 90% of total vanadium amount, mainly be present in illite and limonite with the isomorphism form.The ore structure is mainly crystalline-granular texture, argillaceous texture, micro-scale-argillaceous texture; Cryptocrystalline or microcrystalline texture, idiomorphism-hypidiomorphic granular texture, framboidal texture, metasomatic texture etc.Structure of ores mainly contains lamellar structure, massive structure, impregnation structure, band impregnation structure, concretionary structure etc.
For navajoite, generally all adopt traditional metallurgical technology directly to extract vanadic anhydride from contain the vanadium raw ore, this process environments is seriously polluted, and V leaching rate is low, contaminated environment not only, and also production cost is high.
Summary of the invention
The technical problem to be solved in the present invention is, too high for overcoming in existing metallurgical technology acid consumption, the defective such as production cost is too high, and environmental pollution is serious, propose a kind of from the high-calcium type navajoite beneficiation method of enrichment vanadic anhydride, it adopts technique of preparing cheaply, effectively improves the grade of metallurgical vanadium extraction raw material, reduces the acid consumption of metallurgical vanadium extraction, the treating capacity of compression smelting material, reduce and smelt investment, reduce the unit product production cost, environmental contamination reduction.
Technical scheme of the present invention is:
A kind of beneficiation method from high-calcium type navajoite enrichment vanadic anhydride, the main chemical of high-calcium type navajoite raw ore is (%): V
2O
50.70～1.10, CaO 8～12, MgO 4～8, SiO
238～42, Al
2O
38.5～10.5, TFe 2～5, TC 3～6, S 0.3～0.5, surplus is other natural commensal; It is characterized in that, the method comprises the following steps:
Be 1) 10mm-15mm with high-calcium type navajoite crushing raw ore to particle diameter, then be milled to-the mineral aggregate weight of 0.074mm accounts for this ball milling mineral aggregate gross weight 70%～80%;
2) product that above-mentioned ball milling is obtained, after containing vanadium mineral inhibitor and 600g～1000g calcium mineral collector by mineral aggregate interpolation 2000g～4000g pH value adjusting agent per ton, 800g～1800g, get flotation pulp, then obtain calcium concentrate and vanadium concentrate by one thick two single-minded flotation of sweeping.
Described pH value adjusting agent is sodium carbonate.
The pH value of described flotation pulp is 8～9.5.
The described vanadium mineral inhibitor that contains is waterglass.
Described calcium mineral collector is oleic acid, enuatrol or tall oil.
Below the present invention will be further explained:
Technical solution of the present invention mainly comprises ore grinding and flotation:
1) ore grinding.Be 10mm-15mm with being crushed to particle diameter in high-calcium type navajoite raw ore, then be milled to-the mineral aggregate weight of 0.074mm accounts for this ball milling mineral aggregate gross weight 70～80%;
Mainly compose due to the vanadium in raw ore in the clay minerals such as Iron Oxide Minerals such as being stored in mica mineral, limonite and kaolinite, and Calcium magnesium minerals dolomite, calcite etc. do not contain vanadium, pass through ore grinding, realize separating of mica mineral and Calcium magnesium minerals, contain vanadium mineral and do not contain the vanadium mineral basic monomer and dissociate thereby reach.
2) flotation.The product that above-mentioned ball milling is obtained directly enters flotation, adopts the selected technological process with once purging selection of one roughing, twice, and floatation concentration is 15～30%, and the mash acid alkalinity of whole floatation process remains on pH value 8～9.5.The Calcium magnesium minerals such as dolomite, calcite as the froth pulp emersion, are contained the silicate such as vanadium mineral mica and stay in groove as the vanadium concentrate.
Inhibitor waterglass of the present invention by hydrolysis and polymerization, forms electronegative silicic acid micelle and is dissociated into silicate SiO (OH) in the aqueous solution
3And SiO
2(OH)
2 2-Or comprehensive silicon acid group Si
4O
6(OH)
6 2-Deng the hydrolysis component, polymerization also can occur in silicate, aggregate into bimolecular, three molecules or more macromolecular polymer, because they have identical acid group with silicate minerals such as mainly containing the vanadium mineral mica, thereby be easier to occur suction-operated in the surface ratio of the silicate minerals such as mica.When silicate component strongly hydrophilic due to the silicic acid component after absorption occurs mineral surfaces, strengthen the inhibitory action that mica group is contained vanadium mineral.
Oleic acid of the present invention or enuatrol belong to the anion collecting agent, collecting agent is had an effect with the purpose mineral surfaces with electrostatic force, must make purpose mineral surfaces positively charged, be slurry pH＜PZC (mineral isoelectric point), also require in addition the major part of collecting agent own to be dissociated into anion, be slurry pH＞pKa, that is to say make this anion collecting agent to the purpose mineral take the pH scope of electrostatic force useful effect as pKa＜pH＜PZC.The dissociation constant Ka value of oleic acid and enuatrol is respectively 1 * 10
-5With 1 * 10
-6, the PZC of the main flotation purpose mineral calcite of this ore is 9.5 left and right, and the PZC that mainly contains the vanadium mineral mica is 0.4.Therefore, make slurry pH reach 8～9.5 left and right by adding sodium carbonate, add waterglass to strengthen containing the inhibition of the silicate minerals such as vanadium mineral mica, then add oleic collector can be effectively with the calcium mineral that do not contain vanadium emersion successfully, in groove, the vanadium grade that contains of product is improved and make, and reaches to contain vanadium mineral and the purpose that does not contain vanadium mineral and effectively separate.
Compared with prior art, advantage of the present invention is:
1, the present invention is a kind of beneficiation method from high-calcium type navajoite enrichment vanadic anhydride, it is a kind of low-cost beneficiation method, remove most of calcium mineral in the vanadium raw ore through ore dressing, obtain calcium concentrate and vanadium concentrate, this vanadium concentrate can reduce the treating capacity of follow-up metallurgical vanadium extraction raw material and improve the grade of metallurgical vanadium extraction raw material.
2, adopt this method to process and contain V
2O
50.70～1.10%, contain CaO 8～12%, contain the navajoite of MgO4～8%, flotation vanadium concentrate is through chemical analysis V
2O
5Grade can reach more than 1.40%, contain CaO below 1.50%, V
2O
5The rate of recovery can reach more than 90%, and the calcium removal efficiency can reach more than 90%.
3, the method can reduce the subsequent smelting investment, reduces the unit product production cost.
Description of drawings
Fig. 1 is the ore grinding-flotation beneficiation process chart of a kind of embodiment from high-calcium type navajoite enrichment vanadic anhydride of the present invention.
The specific embodiment
Raw ore is that Xingshan County gingko garden, Hubei Province silver navajoite belongs to the high-calcium type navajoite, and in ore, callable valuable component is mainly vanadic anhydride.In ore, pentoxide content is 0.96%, and the direct vanadium extraction production cost of raw ore is high, and enterprise is difficult to profit.The present invention is directed to this ore deposit and adopt the beneficiation enrichment vanadic anhydride, the technique of high-quality vanadium concentrate is provided for smelting vanadium extraction.
Raw material: Xingshan County gingko garden, Hubei Province navajoite, its main chemical is (%):
| V 2O 5 | CaO | MgO | SiO 2 | Al 2O 3 | TFe | TC | S |
| 0.96 | 9.95 | 5.86 | 39.86 | 9.68 | 2.66 | 4.57 | 0.36 |
Technological process:
1) with high-calcium type navajoite crushing raw ore to particle diameter 2mm, then be milled to-0.074mm mineral aggregate weight accounts for this ball milling mineral aggregate gross weight 70～80%, this ball milling product is as the feed of flotation operation;
3) add sodium carbonate 3000g by flotation mineral aggregate per ton, flotation pulp pH value is 9.5, after waterglass 800～900g and oleic acid 700～800g, obtains calcium concentrate and vanadium concentrate by one thick two single-minded flotation of sweeping, and this vanadium concentrate is as the raw material of smelting vanadium extraction;
Mineral processing index: contain V through this vanadium concentrate of chemical analysis
2O
51.43%, contain CaO 1.52%, V
2O
5The rate of recovery 94.46%, calcium removal efficiency 90.45%.
Claims (1)
1. beneficiation method from high-calcium type navajoite enrichment vanadic anhydride, the main chemical of high-calcium type navajoite raw ore is (%): V
2O
50.70 ~ 1.10, CaO 8 ~ 12, MgO 4 ~ 8, SiO
238 ~ 42, Al
2O
38.5 ~ 10.5, TFe 2 ~ 5, TC 3 ~ 6, S 0.3 ~ 0.5, surplus is other natural commensal; It is characterized in that, the method comprises the following steps:
Be 1) 10mm-15mm with high-calcium type navajoite crushing raw ore to particle diameter, then be milled to-the mineral aggregate weight of 0.074mm accounts for this ball milling mineral aggregate gross weight 70% ~ 80%;
2) product that above-mentioned ball milling is obtained, after containing vanadium mineral inhibitor and 600g ~ 1000g calcium mineral collector by mineral aggregate interpolation 2000 g ~ 4000g pH value adjusting agent per ton, 800g ~ 1800g, get flotation pulp, then obtain calcium concentrate and vanadium concentrate by one thick two single-minded flotation of sweeping; Wherein, the Calcium magnesium minerals such as dolomite, calcite as the froth pulp emersion, are contained the silicate such as vanadium mineral mica and stay in groove as the vanadium concentrate;
Described pH value adjusting agent is sodium carbonate;
The pH value of described flotation pulp is 8 ~ 9.5;
The described vanadium mineral inhibitor that contains is waterglass;
Described calcium mineral collector is oleic acid, enuatrol or tall oil.
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| CN103706465B (en) * | 2013-12-27 | 2015-07-01 | 武汉理工大学 | Method for selecting preconcentration vanadium from high-calcium type stone coal in flotation mode |
| CN104060108B (en) * | 2014-06-10 | 2016-10-05 | 中南大学 | A kind of method extracting vanadium from high calcium siliceous shale containing vanadium |
| CN104148161B (en) * | 2014-08-06 | 2016-09-14 | 昆明理工大学 | A kind of bone coal navajoite acidity that reclaims soaks the method for fine beans in slag |
| CN104941791B (en) * | 2015-07-07 | 2017-06-16 | 湖南有色金属研究院 | A kind of beneficiation method of weathering type bone coal navajoite |
| CN110302904B (en) * | 2019-06-28 | 2021-02-02 | 武汉理工大学 | Calcium-reducing purification method for high-grade basic magnesium carbonate ore |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269353A (en) * | 2008-05-05 | 2008-09-24 | 广州有色金属研究院 | Beneficiation method for recycling scheelite from tungsten ore rich in mispickel |
| CN101371998A (en) * | 2008-08-27 | 2009-02-25 | 花垣县强桦矿业有限责任公司 | Flotation method of low ore grade manganous carbonate ore |
| CN101935768A (en) * | 2010-09-16 | 2011-01-05 | 中南大学 | Method for comprehensively recovering carbon from extraction of vanadium from stone coal |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269353A (en) * | 2008-05-05 | 2008-09-24 | 广州有色金属研究院 | Beneficiation method for recycling scheelite from tungsten ore rich in mispickel |
| CN101371998A (en) * | 2008-08-27 | 2009-02-25 | 花垣县强桦矿业有限责任公司 | Flotation method of low ore grade manganous carbonate ore |
| CN101935768A (en) * | 2010-09-16 | 2011-01-05 | 中南大学 | Method for comprehensively recovering carbon from extraction of vanadium from stone coal |
Non-Patent Citations (2)
| Title |
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| 姚金江等.高钙低品位石煤提取五氧化二钒新工艺.《湖南有色金属》.2009,第25卷(第6期),21-23,61. |
| 高钙低品位石煤提取五氧化二钒新工艺;姚金江等;《湖南有色金属》;20091231;第25卷(第6期);21－23，61 * |
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