CN103498047A - Process for extracting vanadium through alkaline leaching conducted after stone coal oxidizing roasting - Google Patents
Process for extracting vanadium through alkaline leaching conducted after stone coal oxidizing roasting Download PDFInfo
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- CN103498047A CN103498047A CN201310503062.XA CN201310503062A CN103498047A CN 103498047 A CN103498047 A CN 103498047A CN 201310503062 A CN201310503062 A CN 201310503062A CN 103498047 A CN103498047 A CN 103498047A
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- leaching
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- stone coal
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Abstract
The invention relates to a process for extracting vanadium through alkaline leaching conducted after stone coal oxidizing roasting, and belongs to the technical field of metallurgy and chemical industry. The process is characterized by including the steps of firstly, grinding stone coal ore till the 200-mesh particles accounts for about 80% of the total amount, adding water to form balls, and conducting high-temperature roasting in a flat kiln; secondly, using NaOH and sodium carbonate to conduct leaching together in the vanadium leaching process, and conducting leaching for three hours at the temperature lower than 95 DEG C, wherein the massic volume ratio of stone coal roasted product to leaching liquid is 1g/ml to 3g/ml, the additive amount of the NaOH is 40g/L, and the additive amount of the sodium carbonate is 13.5g/L; thirdly, enabling the stone coal to enter a purifying pool after primary leaching and washing are conducted so that the solid-liquid separation can be achieved, stacking and storing the stone coal balls, enabling lixivium to directly flow back to be used for leaching vanadium of newly added stone coal, adding leaching agents to the secondary lixivium according to the proportion of the NaOH to the leaching liquid, namely, 13.5g/L and the proportion of the sodium carbonate to the leaching liquid, namely, 4.5g/L, and enabling the product to flow back to be used for leaching vanadium of stone coal balls which are added for the third time. The process has the advantages of being small in pollution, high in vanadium extraction rate, few in heavy metal impurities produced in the leaching process, small in water consumption and the like, and has certain economic benefits under the present technical condition.
Description
Technical field
The present invention relates to the technique of alkaline-leaching and vanadium extraction after a kind of bone coal oxidizing roasting.Specifically, relate to the vanadium extract technology that the compound alkali of a kind of NaOH and soda ash soaks, leach liquor recycles, belong to the chemical metallurgy technical field.
Background technology
Vanadium is a kind of important metal, is widely used in metallurgy, aerospace, electronics, chemical industry, medicine and other fields, is the important Chemicals of China.Under current technical qualification, the navajoite resource that can exploit and utilize mainly contains vanadium titano-magnetite and bone coal.V in bone coal
2o
5content is generally 0.13～1.2%.Vanadium in bone coal is the insoluble trivalent vanadium V(III with soda acid mainly) and tetravalence vanadium V(IV) for mainly there being form, and V (III) accounts for the overwhelming majority.The key of extracting vanadium from stone coal is that the vanadium existed with forms such as absorption or isomorphs in bone coal is transferred in solution and gone, and then obtains product V by operations such as enrichment, removal of impurities, calcinings
2o
5.
At present, industrial general by the method vanadium extraction of leaching after first roasting.In roasting process, select NaCl, NaCO
3, Na
2sO
4as additive, be conducive to the decomposition of ore and the conversion of vanadium Deng sodium salt, the Cl produced after NaCl decomposes
2, the gas such as HCl has katalysis to the conversion of vanadium, under the acting in conjunction of high temperature, by trivalent vanadium V(III) be oxidized to high price and form water miscible vanadate.Common vanadium leaching method has water logging, acidleach and alkali to soak.Traditional sodium roasting-water logging process for extracting vanadium, low to the working condition requirement, technical process is simple, and cost is low, and capital recovery is fast, is applicable to very much small business and manages, but also have the shortcomings such as the vanadium extraction yield is low, seriously polluted, production environment is poor simultaneously.
Oxidizing roasting refers to does not add the additives such as sodium salt, calcium salt in the bone coal roasting process, and maturing temperature is usually at 750～850 ℃.The effect of oxidizing roasting is to make the vanadium of various valence states in bone coal to be oxidized to as far as possible the Vanadium Pentoxide in FLAKES of high valence state, Vanadium Pentoxide in FLAKES again with material in reactive metal oxide generate the vanadate of water soluble, acid or alkali.The consumption of bone coal sodium salt in the sodium roasting process generally accounts for 20%～30% of raw ore, and oxidizing roasting, owing to not using sodium salt, calcium salt, can be saved a part of expense, does not produce Cl simultaneously
2, the dusty gas such as HCl, be a kind of cleaner production technique.But oxidizing roasting, with respect to sodium roasting, turns the rate of soaking lower, one time the water logging leaching yield only has 40% left and right.
The oxide compound that in bone coal, common metal oxide is calcium, magnesium, iron, sodium, the sodium salt generated with Vanadium Pentoxide in FLAKES is mainly sodium vanadate (Na
3vO
4), sodium pyrovanadate (Na
4v
2o
7), sodium metavanadate (Na
2vO
3), formed magnesium salts is metavanadic acid magnesium (MgOV
2o
5), pyrovanadic acid magnesium (2MgOV
2o
5), positive vanadic acid magnesium (3MgOV
2o
5), the equal water soluble of the sodium salt of vanadium and magnesium salts.Formed calcium salt is mainly metavanadic acid calcium (CaOV
2o
5), pyrovanadic acid calcium (2CaOV
2o
5), positive vanadic acid calcium (3CaOV
2o
5), formed molysite is mainly positive ferric vandate (FeVO
4).The calcium salt of vanadium and molysite solubleness in water is very little, can be dissolved in dilute sulphuric acid and alkaline solution.V
2o
5for intermediate oxide, be soluble in alkaline solution, use NaOH solution as leach liquor, leaching yield can reach more than 80%.Oxidizing roasting-alkali soaking technology has advantages of that V leaching rate is high, it is lighter to pollute, and this technique is in operation and mainly has that the alkali consumption is large, water resources consumption large, vanadium solution needs the problems such as silica removal at present.
Summary of the invention
The objective of the invention is to overcome the technical deficiencies such as the V leaching rate existed at present is low, atmospheric pollution serious, the water resources consumption amount is large in process for extracting vanadium from stone coal, provide a kind of V leaching rate higher, produce pollute less, leaching agent and the few vanadium extract technology of water consumption.
The technical scheme that adopted to achieve the object of the present invention is: when 1) bone coal navajoite after coarse crushing being milled to 200 orders and accounting for 80% left and right, add a certain amount of tap water, do not add the additives such as sodium salt, the stone coal mine ball that to make particle diameter on the disc type nodulizer be 8～15mm; 2) by the ore deposit ball in flat kiln in 750～850 ℃ of lower roasting 3～4h, in roasting process, keep to ventilate and material is heated evenly, in taking out more than 600 ℃, naturally cooling in air; 3) by the ore deposit ball fragmentation after roasting, add compound alkali leaching liquid (NaOH concentration 40g/L, soda ash 13.5g/L), leaching liquid is 3:1 (ml:g) with the ratio of bone coal calcining, under 95 ℃, leaches 3h; 4) leach liquor is separated with calcining, the leach liquor recycle as the next batch roasting after the leach liquor of ore deposit ball, after solid-liquid separation, the ratio that adds NaOH13.5g, soda ash 4.5g in every premium on currency in leach liquor is added leaching agent, as the leach liquor of the 3rd batch of ore deposit ball, afterwards leach liquor is collected.Calcining after leaching is stored up with after twice of tap water drip washing, and leacheate imports after leach liquor standing.5) leaching liquid obtains meeting the Vanadium Pentoxide in FLAKES of Industrial products purity requirement through standing, adjusting pH, silica removal, ion-exchange, ammonium salt precipitation, high-temperature calcination.
After the high-temperature roasting through 800 ℃ of left and right, illitic octahedron is disintegrated, and crystal is destroyed, and vanadium is released and oxidation, and the silicon in mineral and aluminium are separately converted to the oxide compound of sial.Be wrapped in after vanadium in calcining is oxidized in the oxide compound of sial, dissolve after at first the oxide compound of these sial contacts with alkali lye, vanadium just can leach from calcining.Leaching mechanism roughly as shown in the formula:
SiO
2+2NaOH=NaSiO
3+H
2O (1)
Al
2O
3+2NaOH=2NaAlO
2+H
2O （2）
V
2O
5+6NaOH=2Na
3VO
4+3H
2O （3）
Because alkali lye is easy to react with the main component silicon in bone coal, stone coal mine destructurized, more easily leach vanadium, and the alkali leaching yield is higher, generally can reach more than 80%.Oxidizing roasting, owing to not adding the additive such as sodium salt, has therefore been saved the expense of this part, can not produce Cl simultaneously
2, the pollution gas such as HCl, Pollutant Treatment is simple, is high, the lower-cost process for cleanly preparing of a kind of bone coal vanadium resource utilization ratio.In the leaching process of vanadium, used part soda ash to replace NaOH, this not only can reduce the cost of leaching agent, and due to CO
3 2-existence, make some can not be by OH
-the vanadic acid calcium dissolved has leached in solution, and under identical alkali consumption, leaching yield has brought up to 88.6% by 80.2%.After once leaching, the vanadium concentration in leach liquor is 4.0g/L, and now vanadium concentration is low not only is unfavorable for follow-up purification and impurity removal and vanadium enrichment, and has wasted a large amount of water resourcess.After three circulating leachings of employing, leach liquor vanadium concentration approaches 11.8g/L, and water consumption is from 3m
3/ t is reduced to 1m
3/ t has also reduced usage quantity and the quantity of wastewater effluent of leach liquor when reducing water resources consumption.As can be seen here, change processing method and have advantages of that resource consumption is few, leaching yield is high, the generation pollution is few, there is certain prospects for commercial application.
The accompanying drawing explanation
Fig. 1 is the process flow sheet that bone coal oxidizing roasting-alkali soaks
Embodiment
Below in conjunction with embodiment, content of the present invention is further elaborated.
According to operating procedure method of the present invention, adopt the bone coal navajoite of Hunan Mou Fan factory, the process for extracting vanadium flow process shown in by reference to the accompanying drawings, carry out the oxidizing roasting of bone coal navajoite-alkali leaching process, and its method steps is as follows:
1) pre-treatment of bone coal navajoite and oxidizing roasting
At first by the bone coal navajoite coarse crushing, then levigate in dry ball, making granularity by sub-sieve is that 200 purpose bone coals reach 80% left and right, add appropriate tap water, the stone coal mine ball that to make particle diameter on the disc type nodulizer be 8～15mm, dry 2h under 115 ℃, by the ore deposit ball in flat kiln in 750～850 ℃ of lower roasting 3～4h, in roasting process, keep ventilation and material to be heated evenly, in taking out more than 600 ℃, naturally cooling in air.
2) the recycle process of the leaching of vanadium and leach liquor
Grind after the oxidizing roasting of stone coal mine ball warp, in the ratio of raw ore and leaching liquid 1g:3ml, add leaching liquid, in leaching liquid, the concentration of NaOH and soda ash is respectively 40g/L and 13.5g/L.Heating in water bath leaches 3h under 95 ℃.Carry out solid-liquid separation after leaching, through actual measurement, once leaching V leaching rate in bone coal is 88.6%, and in leach liquor, the concentration of vanadium is 4.0g/L.Through refluxing as the leaching liquid of second batch stone coal mine containing vanadium leachate of solid-liquid separation, leach 3h equally under 95 ℃, secondary V leaching rate 80.5%, leach liquor vanadium concentration 7.63g/L.Add NaOH13.5g/L, soda ash 4.5g/L in leach liquor through the secondary circulation utilization.Leach for three times, three times leaching yield is 81.2%, leach liquor vanadium concentration 11.79g/L.After calcining drip washing after solid-liquid separation, store up, leacheate is partly for the bone coal balling-up, and part is for leaching.Leach SiO in the circulating leaching liquid produced
232.46g/L, after adding sulfuric acid adjusting pH9～10, add immediately certain reagent, stir 1h after solution is heated to 90 ℃ and filter silica removal, adopt the V in ion-exchange techniques enrichment leach liquor
2o
5, the desorbed solution of generation adds ammoniacal liquor, and filtration washing obtains red vanadium cake, at 550 ℃ of calcining 2h, the V produced
2o
5>=98.0%, reached the GB3283-87 quality standard.In three times are leached, average leaching yield has reached 83.4%.
Claims (4)
1. the technique of alkaline-leaching and vanadium extraction after a bone coal oxidizing roasting, it is characterized in that soaking in process and using NaOH and soda ash to make leaching agent simultaneously at alkali, three uses of leach liquor circulation are also added appropriate alkali for the third time, the method has reduced the consumption of reagent and water, and makes vanadium concentration in leach liquor improve 12%.
2. the technique of alkaline-leaching and vanadium extraction after a kind of bone coal oxidizing roasting according to claim 1 is characterized in that comprising the following steps:
A. grind after the oxidizing roasting of stone coal mine ball warp, in the ratio of bone coal calcining and leaching liquid mass volume ratio 1:3g/ml, add leaching liquid, under 95 ℃, leach 3h.In leaching liquid, the concentration of NaOH and soda ash is respectively 40g/L and 13.5g/L.
B. through the leaching liquid as the second batch stone coal mine containing the vanadium leachate backflow of solid-liquid separation, leach 3h equally under 95 ℃.Add NaOH13.5g through every liter of the leach liquor of secondary circulation utilization, soda ash 4.5g, for the leaching of the 3rd batch of stone coal mine, the calcining after solid-liquid separation is stored up after drip washing, and leacheate is partly for the bone coal balling-up, and part is for leaching.
3. the technique of alkaline-leaching and vanadium extraction after a kind of bone coal oxidizing roasting according to claim 2 is characterized in that in leach liquor using NaOH and soda ash simultaneously, and in leach liquor, the concentration of NaOH and soda ash is respectively 40g/L and 13.5g/L.
4. the technique of alkaline-leaching and vanadium extraction after a kind of bone coal oxidizing roasting according to claim 3, it is characterized in that leach liquor recycles, through the vanadium leachate that contains that alkali soaks afterwards for the first time, reflux as the leaching liquid of second batch stone coal mine, add NaOH_13.5g to every liter of secondary circulation leach liquor, after soda ash 4.5g for the leaching of the 3rd batch of stone coal mine.Calcining after solid-liquid separation is stored up after drip washing, and leacheate is partly for the bone coal balling-up, and part is for leaching.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107299223A (en) * | 2017-08-18 | 2017-10-27 | 湖南隆洲驰宇科技有限公司 | A kind of bone coal is combined alkaline-leaching and vanadium extraction method and its system |
| CN108251661A (en) * | 2018-01-30 | 2018-07-06 | 长春师范大学 | A kind of bone coal navajoite process for extracting vanadium |
| CN115386742A (en) * | 2022-09-30 | 2022-11-25 | 攀钢集团西昌钒制品科技有限公司 | Method for improving concentration of vanadium in vanadium slag calcified roasting clinker leaching solution |
| CN115747527A (en) * | 2022-11-22 | 2023-03-07 | 东北大学 | Vanadium extraction method of stone coal ore fluidized roasting-pressure leaching based on microwave heating |
| CN115747488A (en) * | 2022-11-22 | 2023-03-07 | 东北大学 | Vanadium shale microwave suspension roasting-alkali mixing curing vanadium extraction system and vanadium extraction method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299223A (en) * | 2017-08-18 | 2017-10-27 | 湖南隆洲驰宇科技有限公司 | A kind of bone coal is combined alkaline-leaching and vanadium extraction method and its system |
| CN107299223B (en) * | 2017-08-18 | 2019-04-12 | 湖南隆洲驰宇科技有限公司 | A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system |
| CN108251661A (en) * | 2018-01-30 | 2018-07-06 | 长春师范大学 | A kind of bone coal navajoite process for extracting vanadium |
| CN115386742A (en) * | 2022-09-30 | 2022-11-25 | 攀钢集团西昌钒制品科技有限公司 | Method for improving concentration of vanadium in vanadium slag calcified roasting clinker leaching solution |
| CN115747527A (en) * | 2022-11-22 | 2023-03-07 | 东北大学 | Vanadium extraction method of stone coal ore fluidized roasting-pressure leaching based on microwave heating |
| CN115747488A (en) * | 2022-11-22 | 2023-03-07 | 东北大学 | Vanadium shale microwave suspension roasting-alkali mixing curing vanadium extraction system and vanadium extraction method thereof |
| CN115747527B (en) * | 2022-11-22 | 2024-05-03 | 辽宁东大矿冶工程技术有限公司 | Vanadium extraction method for stone coal mine fluidization roasting-pressure leaching based on microwave heating |
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Application publication date: 20140108 |