CN102230072B - Roasting method for extracting vanadium from vanadium-containing shale - Google Patents

Roasting method for extracting vanadium from vanadium-containing shale Download PDF

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CN102230072B
CN102230072B CN201110156048.8A CN201110156048A CN102230072B CN 102230072 B CN102230072 B CN 102230072B CN 201110156048 A CN201110156048 A CN 201110156048A CN 102230072 B CN102230072 B CN 102230072B
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vanadium
roasting
shale
additive
mass ratio
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CN102230072A (en
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张一敏
付利攀
黄晶
刘涛
陈铁军
包申旭
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Wuhan University of Science and Engineering WUSE
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Wuhan University of Science and Engineering WUSE
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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 roasting method for extracting vanadium from vanadium-containing shale. According to the technical scheme of the invention, the method comprises the following steps of: uniformly mixing vanadium-containing shale raw ore with a vanadium-containing shale extraction roasting additive in a ratio of 1:(0.06 to 0.1), feeding the mixture to a roasting furnace, heating to 850 to 1000 DEG C at a temperature rise rate of 400 to 500 DEG C/h, maintaining the temperature for 1 to 2 hours, then adding the roasted product to dilute sulfuric acid with volume fraction of 4 to 10% in a solid-liquid mass ratio of 1:2, and leaching at 90 to 100 DEG C for 0.5 to 1 hour under the condition of stirring. The preparation method of the vanadium-containing shale extraction roasting additive comprises the steps of: preparing Mg compounds, namely NaClO3, Na2CO3 and CaCO3 and mixing uniformly, wherein the mass ratio of NaClO3:Na2CO3:CaCO3 is 1:1:(4 to 8):(6 to 10); and grinding until the particle size is not more than 0.15 mm. The method provided by the invention increases the leaching rate up to 86% to 87% and has the characteristics of high recovery rate, short roasting period, high leaching speed and little roasting pollution.

Description

A kind of containing vanadium shale vanadium-extracting roasting method
Technical field
The invention belongs to containing vanadium shale vanadium extraction field, particularly relate to a kind of containing vanadium shale vanadium-extracting roasting method.
Background technology
Containing a kind of navajoite resource that vanadium shale is China's uniqueness, reserves are very abundant; V is extracted from containing vanadium shale 2o 5that China obtains one of important channel of vanadium.Be be present in mica mineral with three stable valence states mostly containing the occurrence status of vanadium in vanadium shale, be water insolublely also insoluble to acid, more difficult containing extracting vanadium vanadium shale from the type.Need adopt roasting that vanadium is converted into solvable tetravalence or pentavalent by trivalent, existing roasting extraction vanadium method divides following four kinds of methods:
1, additive-free roasting
This process characteristic does not add any additive in roasting process, directly at high temperature by the oxygen in air, trivalent vanadium is oxidized to pentavalent.This technological process is simple, the obnoxious flavour produced is few, but it is Rock coal containing alum based on adsorbed state that this technique is only suitable for vanadium, and the rate of recovery of Vanadium Pentoxide in FLAKES is not high, and China's major part is all compose with isomorphous form to exist in micaceous structure containing the vanadium in vanadium shale, vanadium shale is contained according to saltless roasting method for this type of, then vanadium recovery can be caused very low, serious waste of resources.
2, calcium salt additive roasting
The additive that this technique uses is generally CaO, Ca (OH) 2, CaCO 3, its advantage is: do not have Cl in production process 2with the pollution of HCl gas, containing the vanadium recovery of vanadium shale, 50 ~ 65% are brought up to minority.But the shortcoming of this technology is the same with saltless roasting method: have very large selectivity to containing vanadium shale ore, the rate of recovery comparatively saltless roasting method improves 10 ~ 20%, due to the selectivity to ore, be not suitable for producing in enormous quantities.
" a kind of method extracting Vanadium Pentoxide in FLAKES from bone coal " (CN 101274778A) discloses the extraction vanadium method of Wingdale (50 ~ 150 order) roasting of a kind of interpolation 5 ~ 12% weight ratios, and the method only uses CaCO 3make additive, composition is simple, but one of roasting section of insulation need at 600 ~ 800 DEG C of decarburization 1 ~ 4h, two sections of insulations need at 800 ~ 1100 DEG C of roasting oxidation 2 ~ 6h, extraction time is 2 ~ 7h, and this method roasting time reaches 3 ~ 10h, and energy consumption is high, and be used alone the roasting of calcium salt additive for vanadium with class matter homophase compose deposit containing vanadium shale, its leaching yield is not higher than 40%.
3, sodium salt additive roasting
This sinter process uses NaCl, Na 2sO 4as additive, and addition reaches 12 ~ 18%, produces a large amount of Cl during roasting 2, HCl and SO 2gas, exhaust emission is large, serious to equipment corrosion.
" a kind of baking composite additive with sodium for extracting vanadium " (CN 1884597) discloses a kind of by sodium-chlor: sodium carbonate: transition metal oxide=1: 1 ~ 2: 0.5 ~ 2%, transition metal oxide can be the oxide compound of manganese, iron, cobalt, nickel.In this additive, NaCl content accounts for 20 ~ 40%, and additive add-on accounts for gross weight 10 ~ 15%, therefore produces chlorine contained exhaust gas contaminative during roasting large.
4, other additive roastings
" navajoite oxidizing roast composite additive and navajoite roasting method " (CN 101503758A) discloses a kind of by CaCO 3, MgCO 3, CaO, Na 2sO 4composition mixture is composite additive.Adopt this additive roasting to be incubated 3 ~ 6h, roasting time is long; In its embodiment, the ripe sample 1 ~ 1.2g of roasting need boil leaching with 50ml 15% concentration sulphuric acid.This method leaching institute acid consumption is large, concentration is higher, brings larger difficulty to later stage wastewater treatment.
" Rock coal containing alum extracts the roasting additive of Vanadium Pentoxide in FLAKES and application method thereof " (CN101492775A) discloses and a kind ofly accounts for the barium compound, barium metal powder or the barium fluxing agent that to weigh 0.5% ~ 2% containing vanadium shale ore, or adds Na again 2cO 3and CaCO 3wherein a kind of, because barium is a kind of virose heavy metal, particularly bariumchloride has severe toxicity, lethal dose is 0.8 ~ 0.9g, therefore the health of baric dust to workman has serious threat, and after leaching, waste water is also containing barium ion, and environmental pollution is large, difficult treatment, therefore be not suitable for adopting barium or its compound as roasting additive.
Summary of the invention
The present invention is intended to overcome existing technological deficiency, object be to provide that a kind of rate of recovery is high, firing cycle is short, leaching velocity is fast and roasting time contaminative little containing vanadium shale vanadium-extracting roasting method.
For achieving the above object, the technical solution used in the present invention is: first in mass ratio will containing vanadium shale raw ore: be 1 containing vanadium shale vanadium-extracting roasting additive: (0.06 ~ 0.1) mixing, insert stoving oven, with ramp to 850 ~ 1000 DEG C of 400 ~ 500 DEG C/h, insulation 1 ~ 2h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 4 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions.
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by the compound of Mg: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (4 ~ 8): (6 ~ 10) prepare burden, mixing, is finely ground to below 0.15mm.
The compound of described Mg is MgO, MgCO 3, Mg (OH) 2, Mg (NO 3) 2in one.
Described belongs to mica type containing vanadium shale containing vanadium shale raw ore, and contained vanadium is composed with lower valency and isomorph form and is stored in the alumina octahedral crystalline network of aluminosilicate.
Owing to adopting technique scheme, the roasting additive that the present invention obtains, its each composition is fully mixed in grinding processes, there is mutual promoting action, form a multicomponent system, can effectively destroy containing roscoelite structure, promote the oxidation containing vanadium shale middle or low price vanadium.
In the present invention, the crystalline network containing roscoelite needs at high temperature could be destroyed, but when temperature is too high, material easily sinters and causes O in air 2be difficult to permeate hinder Low Valent Vanadium turn valency, and material sintering makes vanadium be wrapped not easily to leach, and the compound adding Mg can improve the soft heat point of roasting material, the structure deteriorate containing roscoelite under high temperature can be made to discharge vanadium, material can not be caused again to sinter.This is because adding of Mg, can react with the silicon in material and calcium, generate dystectic compound and be distributed in material, the fusing point of throughout its mass is improved, thus prevent material from sintering.
NaClO in additive 3there is strong oxidizing property, and the O with oxygenizement can be discharged when roasting 2and Cl 2, especially Cl 2can better promote that the oxidation of Low Valent Vanadium turns valency.Another due to NaClO 3addition is very little compared with raw ore amount quality, therefore a small amount of in waste gas Cl 2can be passed through simple process to be absorbed, therefore pollute little.
Na 2cO 3fusing point is 851 DEG C, and during high-temperature roasting, soft heat becomes liquid phase, is liquid-solid reaction, greatly can accelerates speed of reaction when reacting with mineral.Due to Na 2cO 3and CaCO 3decompose during roasting and generate gas CO 2, make material become bulk, be convenient to additive and O 2infiltrate through in mineral and react with vanadium.
During roasting, containing S and O in vanadium shale raw ore 2react and produce SO 2, and by CaCO 3decompose CaO and the SO generated 2reaction generates CaSO 4, SO in waste gas can be reduced 2discharge.Because roasting time is 1 ~ 2h, the roasting time of more existing extraction vanadium method shortens 2 ~ 6h, and extraction time is only 0.5 ~ 1h, shortens 1 ~ 6h, greatly can reduce production cost and shorten the production cycle.
In sum, inside roasting additive, four kinds of additives are mutually promoted reaction, the roasting of Low Valent Vanadium can be made to turn valency rate and be significantly improved.The compound of Mg can ensure at high temperature to destroy the structure of roscoelite and not make material sinter, in conjunction with Na 2cO 3with the alkalescence of CaO, and NaClO 3strong oxidizing property, more effectively can destroy the structure containing roscoelite, vanadium is discharged and oxidized, because additives decompose generates CO 2make material bulk, be convenient to O 2react with the infiltration of additive and vanadium, finally generate the vanadium compound being soluble in acid.
Therefore the present invention is compared with the prior art, has the following advantages:
1, the transformation efficiency of vanadium is high, and addition is few, roasting and extraction time short, can reduce production cost and shorten the production cycle;
2, HCl, Cl in waste gas is reduced 2, SO 2deng the discharge of obnoxious flavour;
3, to the strong adaptability of ore, have good roasting effect for unmanageable mica type containing vanadium shale especially, the leaching yield of Vanadium Pentoxide in FLAKES can reach 83 ~ 87%.
Embodiment
Below in conjunction with embodiment, the invention will be further described, the restriction not to its protection domain.
The vanadium shale raw ore that contains described in this embodiment belongs to mica type containing vanadium shale, and contained vanadium is composed with lower valency and isomorph form and is stored in the alumina octahedral crystalline network of aluminosilicate.Repeat no more in specific embodiment.
Embodiment 1
A kind of containing vanadium shale vanadium-extracting roasting method: first in mass ratio will containing vanadium shale raw ore: containing vanadium shale vanadium-extracting roasting additive 1: (0.06 ~ 0.075) mixing, insert stoving oven, with ramp to 850 ~ 900 DEG C of 400 ~ 500 DEG C/h, insulation 1.5 ~ 2h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 8 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions.Leaching yield can reach more than 83.7%.
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by MgO: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (4 ~ 6): (6 ~ 8) prepare burden, mixing, is finely ground to below 0.15mm.
Embodiment 2
A kind of containing vanadium shale vanadium-extracting roasting method: first in mass ratio will containing vanadium shale raw ore: to be 1 containing vanadium shale vanadium-extracting roasting additive: (0.075 ~ 0.085) mixing, insert stoving oven, with ramp to 900 ~ 950 DEG C of 400 ~ 500 DEG C/h, insulation 1 ~ 1.5h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 4 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions.Leaching yield can reach more than 86.6%.
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by Mg (NO 3) 2: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (6 ~ 8): (8 ~ 10) prepare burden, mixing, is finely ground to below 0.15mm.
Embodiment 3
A kind of containing vanadium shale vanadium-extracting roasting method: first in mass ratio will containing vanadium shale raw ore: to be 1 containing vanadium shale vanadium-extracting roasting additive: (0.085 ~ 0.1) mixing, insert stoving oven, with ramp to 950 ~ 1000 DEG C of 400 ~ 500 DEG C/h, insulation 1 ~ 2h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 4 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions.Leaching yield can reach more than 85.4%.
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by MgCO 3: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (5 ~ 7): (7 ~ 9) prepare burden, mixing, is finely ground to below 0.15mm.
Embodiment 4
A kind of containing vanadium shale vanadium-extracting roasting method: first in mass ratio will containing vanadium shale raw ore: to be 1 containing vanadium shale vanadium-extracting roasting additive: (0.08 ~ 0.09) mixing, insert stoving oven, with ramp to 950 ~ 1000 DEG C of 400 ~ 500 DEG C/h, insulation 1 ~ 2h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 4 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions.Leaching yield can reach more than 86.9%.
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by Mg (OH) 2: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (7 ~ 8): (8 ~ 10) prepare burden, mixing, is finely ground to below 0.15mm.
Compared with the prior art this embodiment, has following positively effect:
The transformation efficiency of vanadium is high, and addition is few, roasting and extraction time short, can reduce production cost and shorten the production cycle; Reduce HCl, Cl in waste gas 2, SO 2deng the discharge of obnoxious flavour; To the strong adaptability of ore, have good roasting effect for unmanageable mica type Rock coal containing alum especially, the rate of recovery of Vanadium Pentoxide in FLAKES can reach 83 ~ 87%.

Claims (2)

1. one kind contains vanadium shale vanadium-extracting roasting method, it is characterized in that first in mass ratio will containing vanadium shale raw ore: be 1 containing vanadium shale vanadium-extracting roasting additive: (0.06 ~ 0.1) mixing, insert stoving oven, with ramp to 850 ~ 1000 DEG C of 400 ~ 500 DEG C/h, insulation 1 ~ 2h; Be that 1: 2 to join volume fraction be in the dilute sulphuric acid of 4 ~ 10% by the calcining after roasting by solid-liquid mass ratio again, agitation leach 0.5 ~ 1h under 90 ~ 100 DEG C of conditions;
Preparation method containing vanadium shale vanadium-extracting roasting additive is: in mass ratio by the compound of Mg: NaClO 3: Na 2cO 3: CaCO 3be 1: 1: (4 ~ 8): (6 ~ 10) prepare burden, mixing, is finely ground to below 0.15mm;
The compound of described Mg is MgO, MgCO 3, Mg (OH) 2, Mg (NO 3) 2in one.
2. according to claim 1 containing vanadium shale vanadium-extracting roasting method, it is characterized in that the described vanadium shale raw ore that contains belongs to mica type containing vanadium shale, contained vanadium is composed with lower valency and isomorph form and is stored in the alumina octahedral crystalline network of aluminosilicate.
CN201110156048.8A 2011-06-10 2011-06-10 Roasting method for extracting vanadium from vanadium-containing shale Expired - Fee Related CN102230072B (en)

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CN102732739B (en) * 2012-06-08 2013-09-18 武汉理工大学 Method for extracting V2O5 from vanadium-containing shale by using chlorination evaporation
CN102925720B (en) * 2012-11-14 2015-02-04 武汉理工大学 Method for extracting vanadium from shale containing vanadium
CN103290238A (en) * 2013-05-30 2013-09-11 武汉科技大学 Method for leaching and extracting vanadium from vanadium-containing shale rocks
CN103614566B (en) * 2013-12-13 2014-12-10 重庆大学 Method for extracting vanadium and chromium from converter vanadium chromium slag
CN109811123B (en) * 2019-04-08 2021-03-09 重庆大学 Method for extracting vanadium by calcium-magnesium composite reinforcement

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CN1236816A (en) * 1999-04-30 1999-12-01 中南工业大学 Technology for comprehensive utilization of V-Ti magnetite
CN101760651A (en) * 2010-03-04 2010-06-30 中南大学 Process for extracting vanadium by acid leaching of stone coal

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CN101760651A (en) * 2010-03-04 2010-06-30 中南大学 Process for extracting vanadium by acid leaching of stone coal

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