CN100582259C - Method for acid hydrolysis, oxidation, conversion and leaching of vanadium after stone coal decarburization - Google Patents

Method for acid hydrolysis, oxidation, conversion and leaching of vanadium after stone coal decarburization Download PDF

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CN100582259C
CN100582259C CN200910042526A CN200910042526A CN100582259C CN 100582259 C CN100582259 C CN 100582259C CN 200910042526 A CN200910042526 A CN 200910042526A CN 200910042526 A CN200910042526 A CN 200910042526A CN 100582259 C CN100582259 C CN 100582259C
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vanadium
stone coal
sulfuric acid
water
bone coal
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CN101476035A (en
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谢桂文
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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 provides a method of leaching vanadium by acid hydrolyzing, oxidizing and converting after stone coal decarburization. The method comprises steps of (1) dry-grinding bone coal into bone coal powder with a diameter of 1-5mm; (2) burning the bone coal powder in a fluidized bed furnace for decarburization; (3) adding sulfuric acid and water with a mass ratio of bone coal powder :sulfuric acid :water of 100:12-22:8-20, stirring uniformly, wet-stacking under the normal temperature and pressure, and the sulfuric acid has a weight percentage concentration of 98%; (4) adding water according to a solid-liquid weight ratio of 1:0.8-2 under a temperature of 60-70 DEG C and the normal pressure, adding oxydant with 0.1-0.5wt% of the bone coal powder, stirring and leaching for 30-120 minutes, adjusting the PH value to 2-3, and filtering the obtained for deslagging.The invention has characteristics of low equipment investment, low energy-consumption, high coefficient of metal recovery high production efficiency, low producing cost and small environmental pollution.

Description

A kind of method of acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization
Technical field
The present invention relates to a kind of method of from bone coal, refining vanadium, particularly relate to the method for bone coal sulfate-adding wet-pile oxidation conversion vanadium extraction under a kind of normal temperature and pressure.
Background technology
Vanadium can improve intensity, toughness, ductility and the thermotolerance of steel, vanadium metal also can be used for fields such as magneticsubstance, cast iron, Wimet, superconducting material and nuclear reactor material, and Vanadium Pentoxide in FLAKES and other vanadium compound are mainly used in the catalyzer of tinting material, sulfuric acid and the petrochemical complex production usefulness of glass and ceramic industry.Along with developing rapidly of metallurgy, chemical industry, the range of application of vanadium is more and more wider.
Vanadium is mainly derived from and contains coulsonite and bone coal.China V 2O 5Gross storage capacity reaches 135330Kt, and the vanadium reserves are 117960Kt in the bone coal, account for 87% of gross storage capacity.Therefore the vanadium of developing in the bone coal is significant.
The material that contains the scherbinaite coal is more numerous and diverse, and the occurrence status of vanadium changes various, mainly contains by the occurrence status classification of vanadium to contain the roscoelite type, contain vanadium loam mould and the intermediate type between two types.The result of study of the Determination of Different Valence States of vanadium in bone coal shows generally have only V (III) and V (IV) to exist in the bone coal raw ore of various places, does not find V (II) and V (v).Except that ashlar coal V (IV) individually is higher than the V (III), vanadium all is based on V (III) (referring to " a non-ferrous metal metallurgy vanadium piece of writing ") in most regional bone coals.The occurrence status of vanadium and Determination of Different Valence States are the bases of process for extracting vanadium research, all process for extracting vanadium researchs all are around how destroying mica and caly structure, change the valence state of vanadium, make the V (III) of indissoluble become the V (IV) of Yi Rong and V (V) and launch, containing the vanadium minerals structure deteriorate must be thorough more, oxidation is abundant more, soak except that rate high more.
The traditional sodium method bake process for extracting vanadium be bone coal under oxidizing atmosphere, bake the weave construction of destroying vanadium minerals with flat kiln high temperature, trivalent or tetravalence vanadium are oxidized to the pentavalent barium oxide, and the Na that decomposes out with sodium salt 2The O effect generates vanadic acid sodium (xNa soluble in water 2OyV 2O 5).This technology shortcoming is that resource utilization is lower than 50%; Flat kiln is discharged a large amount of hydrogenchloride, chlorine and sulfur dioxide flue gas and thick V 2O 5The waste liquid of post precipitation causes severe contamination to environment, is eliminated.
The principle of acid leaching process is under regular hour, temperature and acidity condition, and H+ is entered in the mica lattice, destroys the micaceous lattice, and vanadium is discharged.The V that discharges (III) changes into V (IV) with oxidizer oxygen and is dissolved in the acid, and filter and remove residue obtains blue vanadium sulfate acyl solution.Vanadium sulfate acyl is again through reduction, and----extraction--after back extraction--precipitation---art breading such as calcining, can obtain content and be 98% Vanadium Pentoxide in FLAKES product in neutralization.
Process for extracting vanadium by acid leaching is the developing direction of extracting vanadium from stone coal from now on.At present, acid leaching process vanadium extraction technology has multiple, and technology respectively has relative merits.For example, Chinese patent discloses under a kind of pressure field the method for oxidative conversion of leached vanadium from bone coal for No. 200610011042.0: the industrial sulphuric acid of bone coal, oxygenant and 50 ~ 98% is joined in the autoclave, 100 ~ 300 ℃ of control invert points, under the pressure 1.0MPa condition, acidleach 10 minutes to 240 minutes, the vanadium that directly transforms in the bone coal enters solution, though the leaching index of vanadium can be up to 95%, but the equipment requirements height, investment is big, the energy consumption height.Chinese patent discloses the slaking water logging of heating of a kind of stone coal ash sulfuric acid for No. 90104669.8 and has extracted the method for Vanadium Pentoxide in FLAKES, the vanadium leaching yield is 68%, and this method exists in bone coal and heats in the maturing process, has a large amount of sulfur dioxide gas to disengage, environmental pollution is serious, and shortcoming such as leaching yield is lower.Also have the xenogenesis process for extracting vanadium by acid leaching in the prior art, continuously stirring leached 20 hours, and the vanadium leaching yield is 78%, and this method exists energy consumption big, to shortcomings such as dissimilar ore adaptability are lower.
Moreover existing acid leaching process all requires stone coal powder is milled to quite thin granularity, thereby after leaching, difficulty in filtration is big, and efficient is low, and acidleach churning time in addition is long, thereby the energy consumption height, and production efficiency is low, the production cost height.For example, Chinese patent application 200710035255.1 disclose a kind of from bone coal the method for normal temperature and pressure oxidative conversion of leached vanadium, the fineness requirement of stone coal powder is the 80-120 order, the bone coal agitation leach time after the stacking is 3-4 hour; Chinese patent application 200710118603.1 disclose a kind of under the normal temperature and pressure method of bone coal sulfate-adding wet-pile oxidation conversion of leached vanadium, also need below grinding stone coal to 60 order, the agitation leach time is 3-8 hour.
Summary of the invention
The objective of the invention is to overcome the defective that prior art exists, provide a kind of facility investment few, energy consumption is low, the metal recovery rate height, the production efficiency height, production cost is low, the method for acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization under the few normal temperature and pressure of environmental pollution.
The objective of the invention is to be achieved through the following technical solutions: it may further comprise the steps: (1) becomes grinding stone coal the stone coal powder of particle diameter 1-5mm; (2) use the boiling furnace combustion decarburization; (3) according to quality than stone coal powder: sulfuric acid: the ratio of water=100: 12-22: 8-20 adds sulfuric acid and water, stir, at normal temperatures and pressures, wet heap 5-12 days, described sulfuric acid are that mass percent concentration is 98% sulfuric acid (can be mass percent concentration be 98% industrial sulphuric acid); (4) under 60-80 ℃ (preferred 64-66 ℃) and condition of normal pressure, according to the solid-liquid weight ratio is 1: the ratio of 0.8-2 adds water, and adding is equivalent to the oxygenant of bone coal grain weight 0.1-0.5wt%, agitation leach 30-120 minute (preferred 50-80 minute), adjust pH is to 2-3 (preferred 2.4-2.7), filter and remove residue promptly obtains blue vanadium sulfate acyl solution.
Heap Gao Yi 〉=2 meter.
Described oxygenant of (4) step is oxygenant, for example hydrogen peroxide or a sodium chlorate etc. commonly used in the prior art.
The present invention is in wet heap process, metal oxide and silicate generation thermopositive reaction such as the aluminium in sulfuric acid and the bone coal, potassium, iron, generate a large amount of vitriol, consume a large amount of sulfuric acid, vitriolic concentration decreases, simultaneously the heat that produced of reaction material temperature in the heap is raise and moisture that bone coal is self-contained and Dilution of sulphuric acid process in added moisture and moisture evaporation that reaction generated, sulfuric acid remains higher concentration, at this concentrated acid.Under the effect of high temperature and steam, hydrogen ion enters the mica lattice, and sulfuric acid destroys mica and caly structure, and vanadium discharges from the mica lattice, and the trivalent vanadium that discharges contacts with airborne oxygen, is oxidized to processable tetravalence vanadium; Through the agitation leach of heating, add oxygenant simultaneously again, processable tetravalence vanadium is oxidized to the pentavalent vanadium.
There are following relation in the head grade and the envrionment temperature of the oxidation conversion leaching yield of vanadium of the present invention and vitriolic concentration, material fineness, wet stack height, wet heap time, vanadium:
The wet heap time generally should be more than 7 days, and when sulfuric acid concentration increased to 86%, the oxidation conversion leaching yield of vanadium reached more than 90%, and the wet heap time shortens to 4 days; When sulfuric acid concentration greater than 86% the time, the oxidation conversion leaching yield of vanadium reduces with the increase of sulfuric acid concentration, wet heap time lengthening;
Raw meal particle size is too thin, and it is little that granularity leaches influence to the oxidation conversion of vanadium, but granularity is thin more, for guaranteeing sulfuric acid moistening to the material surface, needs corresponding increasing with the acid amount, and the wet heap time shortens not obvious;
The heap of material is tall and big in the time of 2 meters, and wet stack height is little to the oxidation conversion leaching yield influence of vanadium, and the oxidation conversion that the shape of heap does not influence vanadium leaches;
Ore grade is high more, and the oxidation conversion leaching yield of vanadium is high more, and the ore of different grades is handled under similarity condition, and its tailings grade is more or less the same;
Envrionment temperature is little to the oxidation conversion influence of vanadium in the wet heap, in the practice, only influences the oxidation conversion leaching yield of the thick heap layer of wet heap top layer 5 ~ 10cm winter.
The present invention has the following advantages: 1. used stone coal powder material particles is thicker, needn't pass through ball milling, both can save and purchase the grinding attachment investment, can reduce production costs again; 2. use the boiling furnace combustion decarburization, the heat energy that is produced is utilized by self, has saved investment and the steam coal of building boiler, has improved the ore grade simultaneously, owing to utilize the thermopositive reaction of material self, energy consumption is low; 3. material has been realized the oxidation conversion of vanadium in stacking process, and the process that water logging goes out vanadium is the dissolution process of vanadium in water; The agitation leach time shortens to 30-120 minute, has improved production efficiency; 4. the heat energy that utilizes the boiling furnace combustion decarburization to produce is heated when leaching, and adds the oxygenant of 0.1-0.5%, improves the leaching yield of vanadium, simultaneously the tetravalence vanadium that leaches all is oxidized to the pentavalent vanadium; 5. behind the adjust pH, refilter and remove slag, can reduce the loss of filtration, improve the rate of recovery of vanadium, simplified technology simultaneously vanadium; 6. metal recovery rate height, tailings content of vanadium of the present invention can be low to moderate below 0.1%, and leaching yield reaches as high as more than 90%; 7. environmental pollution is little, and tailings can fully utilize, and the sulfuric acid major part of being added in the production process is transformed into vitriol such as Tai-Ace S 150, vitriolate of tartar and enters tailings, can be used as byproduct and reclaims, and raffinate can be recycled through handling.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1
(1) will contain the vanadium mass percent is that 0.98% bone coal primary ore is dry grinded into the stone coal powder about particle diameter 4mm; (2) use the boiling furnace combustion decarburization, the stone coal vanadium-containing mass percent after the decarburization is 1.12%; (3) according to quality than stone coal powder: industrial sulphuric acid: it is 98% industrial sulphuric acid and water that water=100: 20: 12 adds mass percent concentration, stir, at normal temperatures and pressures, wet heap 8 days, high about 4 meters of heap; (4) be that 1: 1 ratio adds water according to the solid-liquid weight ratio, and add the oxidant hydrogen peroxide that is equivalent to stone coal powder weight 0.2wt%, heat to 65 ℃, agitation leach 60 minutes, adjust pH to 2.5, filter and remove residue obtains blue vanadium sulfate acyl solution.Vanadium leaching yield 91.3%.
Embodiment 2
(1) will contain the vanadium mass percent is that 0.98% bone coal primary ore is dry grinded into the stone coal powder about particle diameter 3mm; (2) with embodiment 1 step (2); (3) according to quality than stone coal powder: industrial sulphuric acid: it is 98% industrial sulphuric acid and water that the ratio of water=100: 15: 10 adds mass percent concentration, stir, at normal temperatures and pressures, wet heap 10 days, high about 3 meters of heap; (4) be that 1: 1.5 ratio adds entry according to the solid-liquid weight ratio, and add the oxygenant chloric acid sodium that is equivalent to stone coal powder weight 0.3%, heat to 60 ℃, agitation leach 50 minutes, adjust pH to 2.1, filter and remove residue obtains blue vanadium sulfate acyl solution.Vanadium leaching yield 80.5%.
Embodiment 3
(1) will contain the vanadium mass percent is that 0.98% bone coal primary ore is dry grinded into the stone coal powder about particle diameter 2mm; , (2) with embodiment 1 step (2); (3) according to quality than stone coal powder: industrial sulphuric acid: it is 98% industrial sulphuric acid and water that the ratio of water=100: 18: 9 adds mass percent concentration, stir, at normal temperatures and pressures, wet heap 7 days, high about 5 meters of heap; (4) be that 1: 1.6 ratio adds water according to the solid-liquid weight ratio, and add the oxygenant chloric acid sodium that is equivalent to bone coal grain weight 0.4%, heat to 66 ℃, agitation leach 75 minutes, adjust pH to 2.6, filter and remove residue obtains blue vanadium sulfate acyl solution.Vanadium leaching yield 89.7%.
Embodiment 4
(1) with embodiment 1 step (1); (2) with embodiment 1 step (2), the stone coal vanadium-containing mass percent after the decarburization is 1.09%; (3) according to quality than stone coal powder: industrial sulphuric acid: it is 98% industrial sulphuric acid and water that the ratio of water=100: 20: 8 adds mass percent concentration, stirs, and at normal temperatures and pressures, wet heap 9 days is piled high 5 meters; (4) be 1: 0.9 water according to the solid-liquid weight ratio, and add the oxygenant chloric acid sodium that is equivalent to bone coal grain weight 0.4%, heat to about 68 ℃, agitation leach 80 minutes, adjust pH to 2.7, filter and remove residue obtains blue vanadium sulfate acyl solution.Vanadium leaching yield 92.6%.
Embodiment 5
(1) with embodiment 1 step (1); (2) with embodiment 1 step (2); (3) according to quality than stone coal powder: industrial sulphuric acid: it is 98% industrial sulphuric acid and water that the ratio of water=100: 22: 7 adds mass percent concentration, stir, at normal temperatures and pressures, wet heap 12 days, high about 5 meters of heap; (4) adding solid-to-liquid ratio is that 1: 1.8 ratio adds water, and adds the oxidant hydrogen peroxide that is equivalent to bone coal grain weight 0.5%, heat to about 64 ℃, agitation leach 100 minutes, adjust pH to 2.5, filter and remove residue, blue vanadium sulfate acyl solution.Vanadium leaching yield 93.6%.

Claims (5)

1, a kind of method of acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization is characterized in that, may further comprise the steps: (1) becomes grinding stone coal the stone coal powder of particle diameter 1-5mm; (2) use the boiling furnace combustion decarburization; (3) according to quality than stone coal powder: sulfuric acid: the ratio of water=100: 12-22: 8-20 adds sulfuric acid and water, stir, at normal temperatures and pressures, wet heap 5-12 days, described sulfuric acid is that mass percent concentration is 98% sulfuric acid; (4) under temperature 60-70 ℃ and condition of normal pressure, be 1 according to the solid-liquid weight ratio: the ratio of 0.8-2 adds water, and adds the oxygenant that is equivalent to bone coal grain weight 0.1-0.5wt%, and agitation leach 30-120 minute, adjust pH was to 2-3, filter and remove residue.
2, the method for acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization according to claim 1 is characterized in that, in described (4) step, described temperature is 64-66 ℃.
3, the method for acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization according to claim 1 and 2 is characterized in that, in described (4) step, the agitation leach time is 50-80 minute.
4, the method for acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization according to claim 1 and 2 is characterized in that, in described (4) step, adjust pH is to 2.4-2.7.
5, the method for acid hydrolysis oxidative conversion of leached vanadium after stone coal decarbonization according to claim 3 is characterized in that, in described (4) step, adjust pH is to 2.4-2.7.
CN200910042526A 2009-01-19 2009-01-19 Method for acid hydrolysis, oxidation, conversion and leaching of vanadium after stone coal decarburization Expired - Fee Related CN100582259C (en)

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CN102010984A (en) * 2010-12-23 2011-04-13 中南大学 Method for extracting vanadium in coal gangue
CN103290215B (en) * 2013-06-17 2015-05-20 长沙矿冶研究院有限责任公司 Method for curing and leaching reinforced stone coal navajoite concentrated acid
CN109112324A (en) * 2018-09-03 2019-01-01 四川省有色冶金研究院有限公司 It is a kind of to leach the method for efficiently strengthening V leaching rate in bone coal in activation

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石煤提钒的工艺评价. 潘勇.矿业快报，第4期. 2007
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