CN105483398A - Vanadium containing mineral curing vanadium extracting method - Google Patents

Vanadium containing mineral curing vanadium extracting method Download PDF

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Publication number
CN105483398A
CN105483398A CN201610020963.7A CN201610020963A CN105483398A CN 105483398 A CN105483398 A CN 105483398A CN 201610020963 A CN201610020963 A CN 201610020963A CN 105483398 A CN105483398 A CN 105483398A
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China
Prior art keywords
vanadium
minerals
containing vanadium
slaking
leaching
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CN201610020963.7A
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CN105483398B (en
Inventor
郭友谦
宁顺明
任建国
佘宗华
徐辉
吴江华
王喜昌
邢学永
邢积光
梁保平
刘国政
韩其磊
徐永先
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Yongshun Tongda Mining Industry Co Ltd
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Yongshun Tongda Mining Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a vanadium containing mineral curing vanadium extracting method. The method comprises the following steps that firstly, rough breaking of a vanadium containing mineral is carried out; then, a certain amount of water, phosphoric acid and concentrated sulfuric acid are added in obtained mineral powder to be evenly mixed; materials mixed with acid are cured at a certain high temperature; and the obtained clinker is leached through water at the normal temperature and normal pressure, and a leaching agent and leaching residues are obtained after liquid and solid separation. By means of the rough particle mineral and curing through adding of phosphoric acid, leaching of vanadium and fine grinding minerals is consistent, meanwhile, leaching of iron in the mineral is restrained, and losses of lateral neutralization vanadium oxide can be avoided. Thus, vanadium extraction is carried out on the vanadium containing material roughly broken, the fine grinding energy consumption is reduced, meanwhile, iron leaching can be restrained, and the later treatment procedure is simplified. Obvious advantages are achieved compared with an existing curing vanadium extracting method.

Description

A kind of containing vanadium minerals slaking extraction vanadium method
Technical field
The invention belongs to the leaching ore deposit technical field in field of hydrometallurgy, particularly relate to one and extract V from containing vanadium minerals 2o 5method.
Background technology
Vanadium is a kind of very important strategic resource.Vanadium is mainly used in Iron And Steel Industry and ceramic industry, in space industry, nuclear industry, bio-pharmaceuticals and vanadium cell etc., have new application.Substantially adopt sodium-salt calcination-solvent extraction-ammonium salt depositing technology flow process from containing vanadium extraction vanadium minerals, this process recovery ratio generally only has 45% ~ 50%, and roasting process produces HCl and Cl 2deng obnoxious flavour, environmental pollution is very serious, is prohibited by country.
In recent years, concentrated acid curing process for extracting vanadium is due to its clean and effective, and more and more studied person payes attention to.CN1049642A Chinese patent literature discloses one " stone coal ash sulfuric acid is mixed acid slaking water logging of heating and extracted Vanadium Pentoxide in FLAKES technical process ".CN101157981A Chinese patent literature discloses one and " controls the method that silicon impurity leaches in navajoite extraction smelting of vanadium ".CN101260464A Chinese patent literature discloses " a kind of stone coal vanadium-extracting ore decomposition method ", and non-patent literature also discloses " the acidizing fired mineral decomposition technique of extracting vanadium from stone coal Sulfur-Vapor of Lower Temperature " (Liu Wanli, " China YouSe Acta Metallurgica Sinica " 05 phase in 2009, P943 ~ P948).CN101921912A Chinese patent literature and " soaking ore deposit technology " (P536) are proposed the two-stage curing leaching method strengthening sour diffusion containing vanadium minerals.CN102191388A Chinese patent literature proposes the method for two-stage curing Strengthen education in " concentrated acid two-stage curing process for extracting vanadium from stone coal ".These curing processes require higher to mineral granularity above, generally need fine grinding process, and in solution, Fe leaches more, and in subsequent oxidation N-process, Fe will separate out and take away loss vanadium.
The fine grinding of material is be unable to do without in traditional hydrometallurgy, dressing and smelting united all the more so, in order to reach efficient extraction, leaching material must be milled down to enough little granularity, make the valuable component in leaching material and leaching agent have enough contact interfaces, ensure that Leaching reaction carries out completely.In decades, the research of reduction energy consumption in field of hydrometallurgy, simple flow operation also mainly concentrates on and optimizes grinding operation aspect.In addition, due to the solid-liquid separation problem that grinde ore brings, be a difficult problem for puzzlement hydrometallurgical operations all the time.Moreover the requirement of environment protection is increasingly strict, and after fine grinding, tailings can not meet the requirement of recycling to granularity, and waste reside comprehensive utilization is difficult to solve always.
The problem of this three aspect above-mentioned; namely high, the trivial operations of energy consumption, environmental hazard are given prominence to; it is basic problem the most outstanding in current vanadium extraction hydrometallurgy; no matter from guaranteeing efficiency; reduce the direct economy factors such as energy consumption to see; or from the indirect economy factor of environment protection, the levigate operation of ore is all the very crux of series of problems in current field of hydrometallurgy.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides that a kind of technical process is simple, energy-saving and cost-reducing, easy to operate, environmental protection, high, the sour consumption of V leaching rate are low and are suitable for the method leached containing vanadium minerals concentrated acid curing of industrial applications.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of containing vanadium minerals slaking vanadium extraction novel method, comprises the following steps:
(1) first slightly break containing vanadium minerals, the powder particle size < 5mm obtained after slightly breaking;
(2) in the rough powder of step (1) gained, add water and the vitriol oil is mixed thoroughly, and add phosphoric acid;
(3) material that mixes and stirs of step (2) gained is carried out high-temperature maturing at least 24h;
(4) the grog water logging of step (3) gained is gone out, obtain after solid-liquor separation containing vanadium infusion solution and leached mud.
The quality > 40% of breeze in 2 ~ 5mm size range obtained after slightly breaking in described step (1).
In described step (2), the addition of water is 6% ~ 10% containing vanadium minerals quality, and the addition of sulfuric acid is containing vanadium minerals quality 10% ~ 20%.Here sulfuric acid addition refers to and to add after sulphuric acid soln bright sulfur acid percentage in reaction system.
In described step (2), phosphoric acid add-on is 1% ~ 2% containing vanadium minerals quality.Here phosphoric acid addition refers to and to add after phosphoric acid solution pure phosphoric acid percentage in reaction system.
In described step (3), the curing time is 24h ~ 72h.
In described step (3), curing temperature is 80 DEG C ~ 160 DEG C.
Be 0.5h ~ 4h with the time controling that water logging goes out in described step (4), liquid-solid ratio >=1:1 during water logging.
The technical scheme of the invention described above is mainly based on following principle: containing vanadium most of in vanadium minerals with the Al in three valence state isomorph forms replacement micas 3+, Ti 3+, Fe 3+etc. entering in mineral lattice, vanadium is wrapped up by silicate, make vanadium oxidation conversion, must destroy its microtexture.In vitriol oil maturing process, acid and mineral occur to react as follows:
MSiO 3+H 2SO 4+H 2O＝MSO 4·2H 2O+SiO 2
(M and V 3+, Al 3+, Ti 3+, Fe 3+plasma)
Mineral are decomposed to form hydrated sulfate, make silicic acid be converted into the SiO of indissoluble simultaneously 2, the exposed out oxidation by air of vanadium, trivalent vanadium changes into the tetravalence vanadium of processable.
The inventive method is broken the normal procedure, and (namely grinding fineness is thinner for thinking, leaching effect is better) raw materials used needs slightly break, powder particle size < 5mm, especially the quality > 40% in 2 ~ 5mm size range can meet vanadium and leach requirement, just because mineral grain is larger, therefore reaction process is slightly longer than extraction time during fine grinding process, but this measure does not affect the economy of the inventive method, greatly can reduce power consume on the contrary, easy and simple to handle, environmental protection, is conducive to the process of tailings.Mix in sour process in slaking simultaneously and add a certain amount of phosphoric acid, promoter action can be had to vanadium extraction, reduce the content of Fe in infusion solution simultaneously.
Compared with prior art, the invention has the advantages that:
(1) process coarse particles of the present invention is containing vanadium minerals, and significantly reduce energy consumption, be beneficial to leaching simultaneously, waste residue more easily processes.
(2) add phosphoric acid in maturing process of the present invention, inhibit the leaching of Fe, improve V leaching rate simultaneously.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment 1:
Somewhere contains vanadium minerals, raw ore main chemical compositions C9.60%, SiO 264.43%, Al 2o 36.10%, V 2o 50.98%, adopt method of the present invention as shown in Figure 1 to process containing vanadium minerals, specifically comprise the following steps:
First will be finely ground to granularity at below 5mm containing vanadium minerals fragmentation, and the mineral quantity of 2 ~ 5mm size fraction ranges accounts for 55%, add the phosphoric acid of water and 85%, make water in reaction system account for containing vanadium minerals quality 8%, phosphoric acid accounts for 1%, mixes thoroughly, add the vitriol oil of 98% again, make sulfuric acid in reaction system account for containing vanadium minerals quality 16%, mix thoroughly, then will mix and stir material under 105 DEG C of curing temperatures slaking for some time (change of curing time is as shown in table 1 below).The grog of gained is gone out 2h with the water logging of liquid-solid ratio 2:1, and after solid-liquor separation, measure the concentration of vanadium in infusion solution, and calculate the leaching yield of vanadium, under equal conditions carry out experiment numbers 5 simultaneously, experiment 5 does not add phosphoric acid, and its result is as shown in table 1.
Vanadium in table 1 embodiment 1 under the different curing time leaches
Numbering Acid consumption/% Curing time/h V leaching rate/%
1 16 8 54.5
2 16 16 70.3
3 16 24 86.8
4 16 48 87.4
5 16 48 83.2
As can be seen from the experimental result of table 1, the coarse particles ore deposit curing time must have time enough to ensure to react completely, maturing process is the process of infiltration-reaction-infiltration, therefore generally than fine grinding mineral, (general fine grinding is to 80-100 order to process coarse particles mineral, fine grinding mineral curing time 8-12 hour) long more than 2 times of curing time, this experimental raw needs more than 24 hours.As can be seen from experiment numbers 4,5, add a small amount of phosphoric acid during slaking, leaching vanadium has certain promoter action.
Embodiment 2:
Somewhere is containing vanadium minerals, and raw ore chemical composition mainly comprises C14.00%, SiO 259.88%, Al 2o 36.72%, V 2o 51.10%, adopt method of the present invention as shown in Figure 1 to process containing vanadium minerals this, specifically comprise the following steps:
First will be finely ground to granularity at below 5mm containing vanadium minerals fragmentation, and the mineral quantity of 2 ~ 5mm size fraction ranges accounts for 55%, add the phosphoric acid of water and 85%, make water in reaction system account for containing vanadium minerals quality 8%, phosphoric acid accounts for 1%, mixes thoroughly, then adds the vitriol oil of 98%, make sulfuric acid in reaction system account for containing vanadium minerals quality 16%, then will mix and stir material under 105 DEG C of curing temperatures slaking for some time (change of curing time is as shown in table 2 below).The grog of gained is gone out 2h with the water logging of liquid-solid ratio 2:1, and after solid-liquor separation, measure the concentration of vanadium in infusion solution, and calculate the leaching yield of vanadium, its result is as shown in table 2.
Under equal conditions carry out experiment numbers 7, experiment 7 is raw materials used is all finely ground to below 0.15mm, does not add phosphoric acid simultaneously.
Table 2: the lower V leaching rate of large or fine granule contrast in embodiment 2
Numbering Acid consumption/% Curing time/h V leaching rate/% Fe g/L in leach liquor
6 16 24 87.5 1.4
7 16 24 88.4 6.8
As can be seen from table 2 experimental result, thick fine mineral slaking, only have the curing time enough, V leaching rate can be more or less the same, but fine particle does not add phosphoric acid when leaching containing vanadium minerals slaking, then in solution, Fe content significantly raises, and this bothers subsequent oxidation neutralizing treatment very much, and iron removal causes the loss of a large amount of vanadium.

Claims (7)

1., containing a vanadium minerals slaking extraction vanadium method, it is characterized in that, comprise the following steps:
(1) first slightly break containing vanadium minerals, the powder particle size < 5mm obtained after slightly breaking;
(2) in the rough powder of step (1) gained, add water and the vitriol oil is mixed thoroughly, and add phosphoric acid;
(3) material that mixes and stirs of step (2) gained is carried out high-temperature maturing at least 24h;
(4) the grog water logging of step (3) gained is gone out, obtain after solid-liquor separation containing vanadium infusion solution and leached mud.
2. one according to claim 1 is containing vanadium minerals slaking extraction vanadium method, it is characterized in that: the quality > 40% of breeze in 2 ~ 5mm size range obtained after slightly breaking in described step (1).
3. one according to claim 1 is containing vanadium minerals slaking extraction vanadium method, it is characterized in that: in described step (3), the curing time is 24h ~ 72h.
4. the one according to claim 1 or 3, containing vanadium minerals slaking extraction vanadium method, is characterized in that: in described step (3), curing temperature is 80 DEG C ~ 160 DEG C.
5. one according to claim 1 is containing vanadium minerals slaking extraction vanadium method, it is characterized in that: in described step (2), the addition of water is 6% ~ 10% containing vanadium minerals quality, and the addition of sulfuric acid is containing vanadium minerals quality 10% ~ 20%.
6. a kind of containing vanadium minerals slaking extraction vanadium method according to claim 1 or 5, it is characterized in that: in described step (2), phosphoric acid add-on is 1% ~ 2% containing vanadium minerals quality.
7. one according to claim 1 is containing vanadium minerals slaking extraction vanadium method, it is characterized in that: be 0.5h ~ 4h with the time controling that water logging goes out in described step (4), liquid-solid ratio >=1:1 during water logging.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107177742A (en) * 2017-06-09 2017-09-19 中南大学 A kind of method that vanadium is extracted from bone coal

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711371A1 (en) * 1987-04-04 1988-10-20 Metallgesellschaft Ag Process for winning V2O5
CN102337412A (en) * 2010-07-22 2012-02-01 北京有色金属研究总院 Process for recovering zinc and iron from steel-making dust of waste galvanized plates
CN103290215A (en) * 2013-06-17 2013-09-11 长沙矿冶研究院有限责任公司 Method for curing and leaching reinforced stone coal navajoite concentrated acid
CN103555972A (en) * 2013-10-23 2014-02-05 北京矿冶研究总院 Method for leaching vanadium from stone coal vanadium ore by sulfuric acid curing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711371A1 (en) * 1987-04-04 1988-10-20 Metallgesellschaft Ag Process for winning V2O5
CN102337412A (en) * 2010-07-22 2012-02-01 北京有色金属研究总院 Process for recovering zinc and iron from steel-making dust of waste galvanized plates
CN103290215A (en) * 2013-06-17 2013-09-11 长沙矿冶研究院有限责任公司 Method for curing and leaching reinforced stone coal navajoite concentrated acid
CN103555972A (en) * 2013-10-23 2014-02-05 北京矿冶研究总院 Method for leaching vanadium from stone coal vanadium ore by sulfuric acid curing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107177742A (en) * 2017-06-09 2017-09-19 中南大学 A kind of method that vanadium is extracted from bone coal
CN107177742B (en) * 2017-06-09 2018-10-19 中南大学 A method of extracting vanadium from bone coal

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