Wet method reclaims the method for vanadium from vanadium ore containing high silicon and high carbon via
Technical field
The present invention relates to a kind of method that from vanadium ore containing high silicon and high carbon via, reclaims vanadium, be specifically related to a kind of from vanadium ore containing high silicon and high carbon via the method for hydrometallurgic recovery vanadium, belong to technical field of wet metallurgy.
Background technology
Vanadium is that a kind of quality is hard, and HMP is nonmagnetic, the light grey metal of flexible.The purposes of vanadium is very extensive, and in Iron And Steel Industry, vanadium steel has that intensity is big, toughness, wear resistance and the good characteristics of solidity to corrosion, and vanadium still is the important component part of multiple alloy in addition.The main vanadium goods of using have deep processed product V in chemical industry
2O
5, NH
4VO
3(ammonium meta-vanadate), NaVO
3And KVO
3Deng.They are applied to catalyzer, ceramic colorant, photographic developer, siccative respectively and produce the raw material of high-purity vanadium oxide or vanadium iron.The vanadium resource reserves of having verified in the world have 98% symbiosis in vanadium titano-magnetite, mainly are distributed in South Africa, Russia, the U.S., China.Each country is according to the difference of navajoite resource, and the technology of its vanadium extraction also differs widely, and abroad mainly is that from crude oil, to come vanadium extraction, China mainly be from vanadium titano-magnetite and bone coal, to extract vanadium.
China extracts vanadium from the higher-grade vanadium titano-magnetite, mainly be from the mine tailing after the vanadium titano-magnetite ironmaking, to reclaim, and in carrying out steel smelting procedure, vanadium enters into the ironmaking slag, from contain vanadium slag, extracts vanadium again.Bone coal also is a kind of very important vanadium resource, and it is the lambskin that carbon content is few, calorific value is low, is again a kind of low-grade many metals mineral intergrowth.The traditional technology of extracting vanadium from stone coal is the sodium-salt calcination method.This method makes low price vanadium wherein be converted into the high price vanadium through the roasting bone coal, and the high price vanadium combines to generate water miscible vannadate again with sodium salt.Concrete method be earlier with the mineral aggregate after the roasting with water logging or acidleach, the step by " precipitating thick vanadium-thick vanadium alkali dissolves-heavy ammonium meta-vanadate-thermolysis-smart vanadium " obtains smart vanadium product again.The advantage of this method is that technical process is simple, and working condition requires low, and equipment requirements is not high, and the time of founding the factory is short, and cost is lower.Its drawback is to discharge a large amount of HCl, Cl that surrounding enviroment is caused severe contamination that be rich in
2Deng the waste gas of corrosive gases, and have also that the recovery is low, comprehensive utilization of resources is poor, the whole process total yield is lower than 45% deficiency, and China forbids this process method basically.In addition, the method for extraction vanadium also has saltless roasting method and calcium salt roasting method from bone coal.The method of saltless roasting is identical with the method for sodium-salt calcination, just in roasting, does not add sodium salt, thereby has significantly reduced the generation of waste gas.But the bone coal complex structure is lower with the leaching yield of this method vanadium.The calcium salt roasting is to replace sodium salt with calcium salt, in roasting process, does not produce HCl, Cl
2Deng obnoxious flavour, eliminated the chlorine contained exhaust gas pollution problem of sodium-salt calcination technology, transformation efficiency increases substantially than saltless roasting.This technology has technical indicator and environmental benefit preferably, but calcium salt roasting process for extracting vanadium has certain selectivity to calcining matter, and there are problems such as transformation efficiency is low, cost is higher in general ore.Particularly to the carbonate and the silicate mixed type navajoite of the higher high silicon and high carbon of silicon, carbon content, because vanadium is the characteristic of lower valency in this type of navajoite, promptly with V
2O
3And VO
2Form exist, when extracting vanadium in order to last method, the recovery of vanadium generally can only reach 34-46%, and cost is higher, is inappropriate for large batch of production.For example, the typical chemical ingredients of China's vanadium deposit is seen table 1.
Table 1
Chemical ingredients |
V
2O
5 |
SiO
2 |
Al
2O
3 |
Fe
2O
3 |
C |
S |
Mo |
P
2O
5 |
Content, % |
0.80 |
68.97 |
5.35 |
4.88 |
13.20 |
2.29 |
0.010 |
0.21 |
Chemical ingredients |
K
2O
|
Ni |
CaO |
MgO |
Zn |
TiO
2 |
Loss on ignition |
|
Content, % |
0.65 |
0.02 |
2.22 |
1.03 |
0.25 |
0.27 |
18.20 |
|
From the chemical composition analysis result, be the low-grade navajoite of carbonaceous silicate-type, the quality percentage composition of silicon-dioxide is up to nearly 70%; The quality percentage composition of carbon reaches more than 13%; The quality percentage composition of Vanadium Pentoxide in FLAKES is at 0.6-1.2%, and the quality percentage composition of Vanadium Pentoxide in FLAKES on average is about 0.80%, in addition; Also other ore body is higher relatively for the content of aluminium, sulphur, calcium, iron, magnesium, potassium etc.; Therefore when adopting ordinary method to reclaim vanadium, because the influence of factors such as the absorption of the parcel of impurity such as silicon, carbon and parcel makes the recovery of vanadium that 32-53% only arranged.
Summary of the invention
The object of the invention is to provide that a kind of recovery is high, cost is lower, be suitable for producing in enormous quantities, not producing HCl, Cl
2Deng obnoxious flavour, the almost free of contamination wet method of environment is directly extracted the method for vanadium from the carbonate of high silicon and high carbon and silicate mixed type navajoite.
The inventive method comprises following process step successively:
1. ball milling ore grinding
Behind ore reduction to 20 order, add water more than wet ball-milling to 200 order.
2. sulfuric acid oxidation leaches
Get the good navajoite powder of the ball milling of certainweight in leaching vat, measure moisture, calculate dry weight; The mass percentage content that adds navajoite dried bean noodles weight 20-40% then is 95% industrial sulphuric acid; The VAL-DROP of navajoite dried bean noodles weight 1-3% and navajoite dried bean noodles weight 1-2.0 water doubly is 85-95 ℃ at extraction temperature, under the condition of stirring velocity for PM 110-120 commentaries on classics; Stirring oxidation leached 4 hours; After the solid-liquid separation, the leached mud employing is carried out the 2nd time with the 1st identical condition leach, the leaching yield of twice leaching is 90-97%.
3. solid-liquid separation
After leaching finishes; With leach liquor and leached mud solid-liquid separation, leached mud divided with the hot water of breeze weight about 50% washs for 2-3 time, with its washing to neutral; Then the leached mud after hot wash is separated with hot wash-water; Adopt pressure filter to press leached mud to carry out liquid-solid separation, the usefulness when water behind the washing leached mud leaches for the 1st time as next flyash, leached mud is stored up.
4. the extraction of vanadium
Measure the content of vanadium in the 1st sulfoxylic acid leach liquor, the 0.5-1 by Vanadium Pentoxide in FLAKES weight in the 1st infusion solution extraordinarily goes into iron powder again, and is heated to 50-80 ℃, stirs to let it react 2 hours, with the pentavalent vanadium (V in the reducing solution
5+) be tetravalence vanadium (V
4+), after question response was accomplished, use quality percentage composition was 30% ammoniacal liquor adjusting pH value to 2.0; At room temperature stir 1-1.5h then; Leave standstill clarification 0.5-1 hour, using mass percent again is that 15% P204+ mass percent is that 7.5% TBP+ mass percent is that 77.5% aviation kerosene mixing solutions extracts Vanadium Pentoxide in FLAKES as extraction agent, and extraction progression is the 3-5 level; The extraction volume ratio is: organic phase/water=1: 2.5-3, final percentage extraction reaches 97-99%.The 2nd time leach liquor recycles as the 1st leach liquor of next batch preparation of ore.
Wherein, P204 representes (2 1 (2-ethylhexyl) phosphoric acid fat); TBP representes (tributyl phosphate); Aviation kerosene (English title: Jet fuel No.3, i.e. No. 3 rocket(engine)fuels) is to be in harmonious proportion a kind of transparent liquid that forms by component such as straight run, hydrogen cracking and unifining and necessary additive.Mainly form by the hydrocarbon compound of different fractions.
5. the vanadium of from organic phase, stripping
Sulphuric acid soln with 1mol/L is stripped to the above-mentioned organic extraction of rich vanadium mutually, makes the volume and organic extraction volume ratio=1 mutually: 5-8 of sulphuric acid soln, and the reextraction number of times is the 2-4 level, and containing vanadium in the anti-stripping agent is 20-30g/L, and stripping rate reaches 98-99%.
6. ammoniacal liquor precipitation
Anti-stripping agent is carried out oxidation with VAL-DROP again, make the vanadium that is reduced into 4 valencys in the solution be oxidized to 5 valency vanadium once more, the add-on of VAL-DROP is 0.5-1 a times of Vanadium Pentoxide in FLAKES weight in the strip liquor; And under 60 ℃ temperature, stir oxidation 1h; After being cooled to room temperature, regulate the pH value to 2.5-3, stir hydrolysis 1-2h with ammoniacal liquor; Generated the ammonium vanadate deposition, the recovery of deposition vanadium can reach 95-99%.Intensification is boiled; Cooling clarification back press filtration; With separating of liquid after vanadium precipitation slag and the precipitation, adopt 60-80 ℃ hot water of breeze weight about 50% to carry out thorough washing 2-3 time again to the vanadium precipitation slag, with impurity such as the small amount of aluminum of cleaning co-precipitation, iron, calcium, magnesium; Post precipitation liquid in lime with the back qualified discharge, washing lotion is returned leaching and is recycled in the flow process.
7. Vanadium Pentoxide in FLAKES preparation
After 110 ℃ of oven dry,, can make pentoxide content to above vanadium precipitation slag at the Vanadium Pentoxide in FLAKES product more than 98% in 550-650 ℃ of roasting 5h.
Wet method of the present invention reclaims the vanadium method from vanadium ore containing high silicon and high carbon via principle is: since this type of navajoite in vanadium with V
2O
3And VO
2Form exists, and is lower valency V
+ 3, V
+ 4, and vanadium is by the characteristic of impurity absorption such as silicon, carbon and parcel, and ore adopts ball mill to pulverize earlier, in sulphuric acid soln, adopts VAL-DROP to leach vanadium as the oxygenant oxidation, makes the V in the navajoite
2O
3And VO
2Be oxidized into V
2O
5, low price vanadium V
+ 3, V
+ 4Be converted into high price vanadium V
+ 5, high price vanadium V
2O
5Combine to generate water miscible V salt sulfate V again with sulfuric acid
2(SO
4)
5, vanadium is with V
+ 5Form enter into leach liquor, Al simultaneously
2O
3, Fe
2O
3, CaO, MgO, ZnO, TiO
2, K
2Impurity such as O are also leached, and have entered into leach liquor, after solid-liquid separation, to the vanadium (V in the leach liquor
5+) become vanadium (V with iron powder reducing
4+); Behind ammoniacal liquor adjusting pH to 2.0; For the vanadium in the sulphuric leachate is separated with impurity such as silicon, iron, aluminium, calcium, magnesium, sulphur; (English name Jet fuel No.3, i.e. No. 3 rocket(engine)fuels are to be in harmonious proportion a kind of transparent liquid that forms by component such as straight run, hydrogen cracking and unifining and necessary additive with P204 (2 1 (2-ethylhexyl) phosphoric acid fat)+TBP (tributyl phosphate)+aviation kerosene.Mainly form by the hydrocarbon compound of different fractions.) as extraction system; Vanadium in the leach liquor extracts, because the partition ratios of impurity in organic phase such as other aluminium that is leached simultaneously, iron, calcium, magnesium, zinc, titanium, potassium are less, is not dissolved in the organic phase; And the partition ratio of vanadium is bigger, thereby realizes vanadium and other separate impurities.For from enrichment the organic extract liquid of vanadium extract vanadium, need strip, make vanadium enter into aqueous phase so that the subsequent recovery vanadium, and extraction agent can be reused, strip from extracted organic phase with the sulphuric acid soln of 1.0mol/L and isolate vanadium V
4+After, be from anti-stripping agent, to reclaim the enrichment vanadium, vanadium is further separated, to the vanadium V in the anti-stripping agent with other impurity in the anti-stripping agent
4+Carry out oxidation with VAL-DROP again, make vanadium V
4+Be oxidized to vanadium V
5+, because of the vanadium in the anti-stripping agent has been reduced into tetravalence vanadium (V
4+), can not precipitate, so earlier will be the tetravalence vanadium (V in the anti-stripping agent with ammoniacal liquor
4+) carry out oxidation with VAL-DROP again, make the tetravalence vanadium (V in the solution
4+) be oxidized to pentavalent vanadium (V once more
5+), adopt strong aqua to come the vanadium in the precipitation solution again, so that vanadium can separate, thereby make ammonium vanadate from anti-stripping agent.Ammonium vanadate makes Vanadium Pentoxide in FLAKES after taking off ammonium through the oven dry roasting again.
The chemical equation of each step is in present method:
(1)V
2O
3+NaClO
3=V
2O
5+NaClO;
(2)4VO
2+NaClO
3=2V
2O
5+NaClO;
(3)V
2O
5+5H
2SO
4=V
2(SO
4)
5+5H
2O;
(4)Al
2O
3+3H
2SO
4=Al
2(SO
4)
3+3H
2O;
(5)Fe
2O
3+3H
2SO
4=Fe
2(SO
4)
3+3H
2O;
(6)CaO+H
2SO
4=CaSO
4+H
2O;
(7)MgO+H
2SO
4=MgSO
4+H
2O;
(8)ZnO+H
2SO
4=ZnSO
4+H
2O;
(9)TiO
2+2H
2SO
4=Ti(SO
4)
2+2H
2O;
(10)K
2O+H
2SO
4=K
2SO
4+H
2O;
(11)V
2(SO
4)
5+Fe=2V(SO
4)
2+FeSO
4;
(12)NaVO
3+NH
3.H
2O=NH
4.VO
3↓+NaOH;
Wherein, the chemical reaction process of step 2 is seen formula (1)-(10), and the chemical reaction process of step 6 is seen formula (11)-(12), and the chemical reaction process of step 7 is seen formula (13).
The invention has the beneficial effects as follows: 1, the recovery is high, for V
2O
5Average grade is 0.85% low-grade navajoite only, after employing present method, and the about 95-97% of the leaching yield of Vanadium Pentoxide in FLAKES; The about 97-99% of percentage extraction; The about 98-99% of back extraction ratio, the about 95-98% of ammonium salt precipitation rate, roasting yield>=98.0%; The total yield of Vanadium Pentoxide in FLAKES is 75-85%, the be up to state standards specification of quality of " GB/T 3283 Vanadium Pentoxide in FLAKESs " of other foreign matter content.The recovery from the navajoite to the Vanadium Pentoxide in FLAKES can reach 87.1-93.3%.2, production cost is low, and 3, can connect production, 4, do not produce HCl, Cl
2Deng obnoxious flavour, but a large amount of washing water recirculation use, not only practiced thrift part of sulfuric acid, VAL-DROP and water, also reduced discharging, and a small amount of unnecessary trade effluent, can adopt qualified discharge after the lime neutralizing treatment, almost pollution-free to environment.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
With the example that is treated to, the inventive method is described further below China somewhere navajoite in the background technology.
Embodiment 1: the wet ball mill of learning from else's experience is crushed to the above navajoite powder of 200 orders in the beaker of 3000mL, wherein dried navajoite powder 1000g, and the quality percentage composition of Vanadium Pentoxide in FLAKES is 0.80%; Add 20g VAL-DROP, 250g quality percentage composition is behind 95% the industrial sulphuric acid and 1800mL water stirring and evenly mixing, to carry out the 1st leaching; Be warming up to 85 ℃, and maintain the temperature at 85-90 ℃, start mechanical stirring; Rotating speed is that PM 115 changes; Agitation leach 4h uses vacuum filtration then, obtains leach liquor 2100mL the 1st time.Adopt above condition that leached mud is carried out the 2nd oxidation again and leach, vanadium quality percentage composition is that 0.04%, twice leaching yield is 95.4% in the 2nd the leaching back slag.With hot water it is washed till through pH test paper check and is neutral, after the solid-liquid separation, leached mud is stored up.The content of measuring Vanadium Pentoxide in FLAKES in the 1st leach liquor is 3.51g/L, adds the iron powder of 7.35g, and is heated to 60 ℃; Behind the stirring reaction 2 hours, be cooled to room temperature, use quality percentage composition is 30% strong aqua adjusting pH value to 2.0; And stirring reaction 1h; After leaving standstill 1h, carry out 3 extractions with 700mL extraction agent [extraction agent is made up of 15% (quality percentage composition) P204,7.5% (quality percentage composition) TBP, 77.5% (quality percentage composition) aviation kerosene], percentage extraction is 97.5%.Sulphuric acid soln 100mL with 1mol/L carries out 2 reextraction to the organic phase of saturated vanadium again, and the content of Vanadium Pentoxide in FLAKES is 69.0g/L in the strip aqueous, and stripping rate is 98.12%.In strip aqueous, add 3.7g VAL-DROP, and under 60 ℃ temperature, stir oxidation 1h, be cooled to room temperature after, regulate pH value to 2.55 with ammoniacal liquor, stirring hydrolysis 2h, vanadium has generated the ammonium vanadate deposition, the vanadium deposition rate is 95.43%.Intensification is boiled, and cooling clarification after-filtration obtains the vanadium precipitation slag; Adopt hot water that the vanadium precipitation slag is carried out 3 washings, precipitated liquid is with discharging with the back in the lime, and washing lotion is returned to leach in the flow process and recycled; The vanadium precipitation slag in 650 ℃ of oxidizing roasting 5h, obtains the Vanadium Pentoxide in FLAKES product of 22.7g after 110 ℃ of oven dry; Vanadium Pentoxide in FLAKES quality percentage composition is 98.32%, oxidizing roasting yield 99.56%, and the recovery from the navajoite to the Vanadium Pentoxide in FLAKES is 87.10%.
Embodiment 2: the wet ball mill of learning from else's experience is crushed to the above navajoite powder of 200 orders in the beaker of 3000mL, wherein dried navajoite powder 1000g, and the quality percentage composition of Vanadium Pentoxide in FLAKES is 1.0%; Add 10g VAL-DROP, 400g quality percentage composition is behind 95% the industrial sulphuric acid and 1000mL water stirring and evenly mixing, to carry out the 1st leaching; Be warming up to 85 ℃, and maintain the temperature at 85-90 ℃, start mechanical stirring; Rotating speed is that PM 115 changes; Agitation leach 4h uses vacuum filtration then, obtains leach liquor 1050mL the 1st time.Adopt above condition that leached mud is carried out the 2nd oxidation again and leach, vanadium quality percentage composition is that 0.04%, twice leaching yield is 96.3% in the 2nd the leaching back slag.With hot water it is washed till through pH test paper check and is neutral, after the solid-liquid separation, leached mud is stored up.The content of measuring the 1st Vanadium Pentoxide in FLAKES in the leach liquor is 9.60g/L, adds the iron powder of 10.0g, and is heated to 60 ℃; Behind the stirring reaction 2 hours, be cooled to room temperature after, using the quality percentage composition is that 30% strong aqua is regulated pH value to 2.0; And stirring reaction 1h; After leaving standstill 1h, carry out 5 extractions with 350mL extraction agent [being made up of 15% (quality percentage composition) P204,7.5% (quality percentage composition) TBP, 77.5 (quality percentage composition) % aviation kerosene], percentage extraction is 99.1%.Sulphuric acid soln 75mL with 1mol/L carries out 4 reextraction to the organic phase of saturated vanadium again, and the content of Vanadium Pentoxide in FLAKES is 88.70g/L in the strip aqueous, and stripping rate is 98.75%.In strip aqueous, add 9.5g VAL-DROP, and under 60 ℃ temperature, stir oxidation 1h, be cooled to room temperature after, regulate pH value to 2.98 with ammoniacal liquor, stirring hydrolysis 2h, vanadium has generated the ammonium vanadate deposition, the vanadium deposition rate is 99.01%.Intensification is boiled, and cooling clarification after-filtration obtains the vanadium precipitation slag; Adopt 300mL hot water that the vanadium precipitation slag is carried out 3 washings, precipitated liquid is with discharging with the back in the lime, and washing lotion is returned to leach in the flow process and recycled; The vanadium precipitation slag in 550 ℃ of oxidizing roasting 5h, obtains the Vanadium Pentoxide in FLAKES product of 29.2g after 110 ℃ of oven dry; Vanadium Pentoxide in FLAKES quality percentage composition is 98.51%, oxidizing roasting yield 99.72%, the recovery 93.30% from the navajoite to the Vanadium Pentoxide in FLAKES.
Embodiment 3: the wet ball mill of learning from else's experience is crushed to the above navajoite powder of 200 orders in the beaker of 3000mL, and (wherein dried navajoite powder 1000g), the quality percentage composition of Vanadium Pentoxide in FLAKES is 1.20%; Add 30g VAL-DROP, 300g quality percentage composition is 95% industrial sulphuric acid and 2000mL water, carries out the 1st time behind the stirring and evenly mixing and leaches; Be warming up to 85 ℃, and maintain the temperature at 85-90 ℃, start mechanical stirring; Rotating speed is that PM 115 changes; Agitation leach 4h uses vacuum filtration then, obtains leach liquor 1900mL the 1st time.Adopt above condition that leached mud is carried out the 2nd oxidation again and leach, content of vanadium is that 0.06%, twice leaching yield is 96.8% in the 2nd the leaching back slag.With hot water it is washed till through pH test paper check and is neutral, after the solid-liquid separation, leached mud is stored up.The content of measuring Vanadium Pentoxide in FLAKES in the 1st leach liquor is 6.06g/L, adds the iron powder of 11.0g, is heated to 60 ℃; Stirring reaction 2 hours, be cooled to room temperature after, using the quality percentage composition is that 30% strong aqua is regulated pH value to 2.0; And stirring reaction 1h; After leaving standstill 1h, carry out 4 extractions with 600mL extraction agent [15% (quality percentage composition) P204+7.5% (quality percentage composition) TBP+77.5 (quality percentage composition) % aviation kerosene], percentage extraction is 98.7%.Sulphuric acid soln 100mL with 1mol/L carries out 3 reextraction to the organic phase of saturated vanadium again, and the content of Vanadium Pentoxide in FLAKES is 110.46g/L in the strip aqueous, and stripping rate is 97.38%.In strip aqueous, add 10g VAL-DROP, and under 60 ℃ temperature, stir oxidation 1h, be cooled to room temperature after, regulate pH value to 2.70 with ammoniacal liquor, stirring hydrolysis 2h, vanadium has generated the ammonium vanadate deposition, the vanadium deposition rate is 96.37%.Intensification is boiled, and cooling clarification after-filtration obtains the vanadium precipitation slag; Adopt 450mL hot water to divide 3 each 150mL that the vanadium precipitation slag is washed, precipitated liquid is with discharging with the back in the lime, and washing lotion is returned to leach in the flow process and recycled; The vanadium precipitation slag in 600 ℃ of oxidizing roasting 5h, obtains the Vanadium Pentoxide in FLAKES product of 35.69g after 110 ℃ of oven dry; The quality percentage composition of Vanadium Pentoxide in FLAKES is 98.78%, oxidizing roasting yield 99.61%, and the recovery from the navajoite to the Vanadium Pentoxide in FLAKES is 89.67%.
Process control condition and data that embodiment is concrete are seen table 2
Table 2 process control parameter condition