CN111334675A - Method for extracting vanadium from low-grade stone coal vanadium ore - Google Patents
Method for extracting vanadium from low-grade stone coal vanadium ore Download PDFInfo
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- CN111334675A CN111334675A CN202010185648.6A CN202010185648A CN111334675A CN 111334675 A CN111334675 A CN 111334675A CN 202010185648 A CN202010185648 A CN 202010185648A CN 111334675 A CN111334675 A CN 111334675A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 157
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 81
- 239000003245 coal Substances 0.000 title claims abstract description 75
- 239000004575 stone Substances 0.000 title claims abstract description 75
- 238000002386 leaching Methods 0.000 claims abstract description 112
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000853 adhesive Substances 0.000 claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 claims abstract description 28
- 239000008188 pellet Substances 0.000 claims abstract description 21
- 238000005507 spraying Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005453 pelletization Methods 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000005056 compaction Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920006158 high molecular weight polymer Polymers 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 26
- 230000032683 aging Effects 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 46
- 239000002253 acid Substances 0.000 description 41
- 229910052500 inorganic mineral Inorganic materials 0.000 description 17
- 239000011707 mineral Substances 0.000 description 17
- 235000010755 mineral Nutrition 0.000 description 17
- 238000002156 mixing Methods 0.000 description 14
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000035515 penetration Effects 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000010454 slate Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
-
- 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
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- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting vanadium from low-grade stone coal vanadium ore, which comprises the following steps: crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm; adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and then adding an adhesive and water for pelletizing to obtain pelletized ore; curing the pellet ore at normal temperature to obtain a cured material; and filling the cured material into a column, spraying dilute sulfuric acid to perform column leaching to obtain vanadium-containing leaching solution. The invention effectively solves the problems that the vanadium extraction process in the prior art has high requirement on the grade of raw ore, the stone coal vanadium ore needs to be ground to a certain fineness, and the aging and leaching of the raw ore after grinding need to be carried out under a certain temperature condition, and is particularly suitable for leaching vanadium in low-grade stone coal vanadium ore.
Description
Technical Field
The invention relates to the technical field of nonferrous metallurgy, in particular to a method for extracting vanadium from low-grade stone coal vanadium ore.
Background
The stone coal vanadium ore is the dominant resource in China, has huge reserves and accounts for the vanadium reserves (V)2O5Calculated) 87% of the total reserves. The grade difference of vanadium in the stone coal vanadium ore in each region is large, wherein the stone coal vanadium ore of which the grade of vanadium is less than 0.5 percent of the boundary grade accounts for 60 percent, and the mass fraction of calcite and carbonaceous materials in the ore is high, so that most of the stone coal vanadium ore belongs to low-grade multi-metal ore.
In the prior art, the vanadium extraction process which is widely applied mainly comprises roasting-weak acid leaching, crude ore strong acid leaching, acid mixing curing leaching and the like. However, the existing vanadium extraction process has high requirements on the grade of raw ore, stone coal vanadium ore needs to be ground to a certain fineness, and meanwhile, the raw ore is ground and then aged and leached under a certain temperature condition, so that not only is heating equipment provided, but also the acid consumption is high.
Therefore, aiming at the occurrence state of the stone coal vanadium ore, how to economically and effectively extract vanadium-containing leachate from the low-grade stone coal vanadium ore which is difficult to treat and prepare high-purity vanadium pentoxide still remains a challenge in the stone coal vanadium extraction industry.
Disclosure of Invention
The embodiment of the invention provides a method for extracting vanadium from low-grade stone coal vanadium ore, which aims to solve the problems that the requirement on the grade of raw ore is high, the stone coal vanadium ore needs to be ground to a certain fineness, and the aging leaching of the ground raw ore needs to be carried out under a certain temperature condition in the vanadium extraction process in the prior art.
The embodiment of the invention provides a method for extracting vanadium from low-grade stone coal vanadium ore, which comprises the following steps:
crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing to obtain pelletized ore;
curing the pellet ore at normal temperature to obtain a cured material;
and filling the aged material into a column, spraying dilute sulfuric acid for column leaching, and performing solid-liquid separation to obtain vanadium-containing leachate and leaching slag.
In a preferred embodiment of the present invention, in the step of obtaining crushed ore, V in the stone coal vanadium ore2O5The content of (B) is not less than 0.3 wt%.
In a preferred embodiment of the present invention, in the step of obtaining the pellet ore, a mass ratio of the concentrated sulfuric acid to the crushed ore is 0.035 to 0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of the water to the crushed ore is 0.05-0.1: 1.
in a preferred embodiment of the present invention, the step of obtaining the pellet ore comprises adding concentrated sulfuric acid to the crushed ore, standing for 24 hours, and adding the binder and water to perform the pellet.
In a preferred embodiment of the present invention, the adhesive is a high molecular polymer having a molecular weight of more than 3000 ten thousand.
In a preferred embodiment of the present invention, in the step of obtaining a clinker, the time for the briquette to be matured at normal temperature is 72 hours or more.
In a preferred mode of the invention, in the step of obtaining the vanadium-containing leaching solution, the concentration of the dilute sulfuric acid is 10-20 g/L.
In a preferred embodiment of the present invention, in the step of obtaining the vanadium-containing leachate, the initial spraying strength of the dilute sulfuric acid is 0.1L/min m or more2The permeation speed of the dilute sulfuric acid is less than or equal to 1L/min-m2。
In a preferred embodiment of the present invention, in the step of obtaining the vanadium-containing leachate, the degree of compaction of the slaked material in column leaching is 8% or less.
In a preferred embodiment of the present invention, in the step of obtaining the vanadium-containing leachate, the time for column leaching the matured material is 30 to 90 days.
The method for extracting vanadium from low-grade stone coal vanadium ore provided by the embodiment of the invention has the following beneficial effects:
(1) the method has low requirement on the content of vanadium in the stone coal vanadium ore, has low requirement on the particle size of the ore, can meet the process requirement when the particle size is less than 15mm, effectively avoids the influence of calcite, carbonaceous materials and the like in the stone coal vanadium ore on the vanadium extraction process, and simultaneously reduces the crushing and grinding cost of the ore;
(2) the pellet ore is cured at normal temperature, and no additional heat-preservation curing equipment is needed, so that the production energy consumption can be obviously reduced, and the production cost can be reduced;
(3) according to the invention, the pellet ore is aged at normal temperature and then is loaded into the column for column leaching, the aging process and the leaching process are both carried out at normal temperature, the concentration of impurity ions in the leaching solution can be effectively reduced, the leaching solution is clear, no additional solid-liquid separation equipment is required for separation, the production cost is effectively reduced, and the purification of the subsequent leaching solution is facilitated.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flow chart of a method for extracting vanadium from low-grade stone coal vanadium ore according to an embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
Referring to fig. 1, the embodiment of the invention discloses a method for extracting vanadium from low-grade stone coal vanadium ore, which mainly comprises the following steps:
101. and (3) crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm.
In the step, most of the stone coal vanadium ores in China are low-grade multi-metal ore, wherein the stone coal vanadium ores with the vanadium grade less than 0.5% of the boundary grade account for 60%, and the ores are generally difficult to process, so that the challenges of the stone coal vanadium extraction industry are still how to economically and effectively extract vanadium-containing leachate from the intractable low-grade stone coal vanadium ores and prepare high-purity vanadium pentoxide.
In this embodiment, the specific crushing process is not limited, and a jaw crusher or a cone crusher or the like may be used to crush the obtained low-grade stone coal vanadium ore to obtain crushed ore with a particle size of less than 15 mm.
The requirement on the particle size of the crushed ore is not high in the step, the particle size of the crushed ore is controlled to be less than 15mm, the process requirement can be met, the problems that the viscosity of slaking leachate is high, the acid consumption is high, the carbon adsorption capacity is strong, the vanadium leaching rate is reduced and the like caused by the fact that calcite, carbonaceous materials and the like with high quality fraction in the stone coal vanadium ore are too fine in particle size can be effectively solved, and the crushing and grinding cost of the ore is effectively reduced.
Preferably, in step 101, V in stone coal vanadium ore2O5The content of (B) is not less than 0.3 wt%.
Specifically, the low-grade stone coal vanadium ore treated by the method in the present example, in which V is2O5The content of the vanadium can be more than or equal to 0.3wt percent, and the requirement of vanadium extraction of low-grade stone coal vanadium ore is effectively met.
102. Adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and then adding an adhesive and water for pelletizing to obtain the pelletized ore.
In the step, concentrated sulfuric acid is added into the crushed ore obtained in the step, and the crushed ore is uniformly stirred. The concentrated sulfuric acid added in the process is industrial-grade concentrated sulfuric acid, and the concentration of the concentrated sulfuric acid is preferably 85-98 wt%.
Then placing for a period of time, adding adhesive and water and carrying out pelletizing operation, thereby obtaining the pellet ore. The adhesive added in the process is a high molecular polymer, and the added water is tap water to meet the requirement.
Preferably, in the step 102, the mass ratio of the concentrated sulfuric acid to the crushed ore is 0.035-0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of water to crushed ore is 0.05-0.1: 1.
specifically, when the pelletizing operation is performed, the mass ratio of concentrated sulfuric acid to crushed ore is preferably 0.035-0.05: 1, the mass ratio of the adhesive to the crushed ore is preferably 0.002: 1, the mass ratio of water to crushed ore is preferably 0.05-0.1: 1.
under the preferred proportion, the mineral particles of the crushed ore, the concentrated sulfuric acid, the adhesive and the water have better mutual matching effect and high wet strength of the mineral particles, so that the phenomenon of argillization or looseness of the mineral particles in the spraying and leaching processes can be effectively avoided, the particles are still intact after the spraying and leaching, the compactness is low, the permeation speed is high, and the leaching is complete.
Preferably, in step 102, concentrated sulfuric acid is added into the crushed ore, and then the crushed ore is placed for 24 hours, and then the binder and water are added for pelletizing.
Specifically, after concentrated sulfuric acid is added into the crushed ore and uniformly stirred, the crushed ore needs to be placed for 24 hours, and then the adhesive and the water are added, so that the concentrated sulfuric acid can be ensured to be fully contacted with ore particles of the crushed ore, and meanwhile, the concentration of reactants is increased, the collision probability of reactant molecules is increased, the reaction probability among the reactants is increased, and the curing process is carried out more completely.
Preferably, in step 102, the adhesive is a high molecular polymer having a molecular weight greater than 3000 ten thousand.
Specifically, the adhesive is preferably a high molecular polymer with a molecular weight of more than 3000 ten thousand, which can ensure that the chain frame of the adhesive is not easy to break in a strong acid system, and has good cementing property for ore particles of crushed ores.
103. And curing the pellet ore at normal temperature to obtain a cured material.
In this step, the pellets obtained in step 102 are aged at a normal temperature, which is a room temperature state in this embodiment.
The pellets are aged at normal temperature due to impurity ions such as Ca at that temperature2+、Fe2+、Fe3+、Al3+、SiO3 2-The leaching is obviously reduced, so that the final leaching solution is clear, the impurities are few, the subsequent extraction process is facilitated, and meanwhile, no additional heat-preservation curing equipment is required in the curing process, so that the production energy consumption can be obviously reduced, and the production cost can be reduced.
Preferably, in step 103, the time for aging the pellets at normal temperature is greater than or equal to 72 hours.
Specifically, the conglomerate is aged for not less than 72 hours at normal temperature, so that the structure of the vanadium-containing mineral can be damaged to the maximum extent, and the leaching rate of vanadium can be improved.
104. And filling the cured material into a column, spraying dilute sulfuric acid to perform column leaching to obtain vanadium-containing leaching solution.
In the step, the cured material obtained in the step 103 is filled into a column, and then diluted sulfuric acid is sprayed for column leaching, so that the vanadium-containing leaching solution is finally obtained. The leachate is clear, and no solid-liquid separation equipment is additionally arranged for separation, so that the production cost is effectively reduced, and the subsequent purification of the leachate is facilitated.
The obtained vanadium-containing leaching solution is subjected to reduction, neutralization, extraction, back extraction, impurity removal, vanadium precipitation, calcination and other processes in sequence to obtain a refined vanadium product V2O5The content is more than 98.50 percent.
Preferably, in the step 104, the concentration of the dilute sulfuric acid is 10-20 g/L.
Specifically, in the column leaching process of the aged material, the concentration of sprayed dilute sulfuric acid is preferably 10-20 g/L, the dilute sulfuric acid at the concentration can effectively dissolve out vanadium released from the aged material, the crystal structure of vanadium-containing minerals can be further destroyed, and vanadium in the vanadium-containing minerals can be further leached out.
Preferably, in step 104, the initial spraying strength of the dilute sulfuric acid is greater than or equal to 0.1L/min-m2The permeation speed of the dilute sulfuric acid is less than or equal to 1L/min m2。
Specifically, the spraying strength of dilute sulfuric acid is strictly controlled during column leaching of the slaked material. The initial spraying strength of the dilute sulfuric acid is controlled to be more than or equal to 0.1L/min m2Then gradually increasing, and measuring the penetration rate and compaction degree of the cured material near the end of spraying to make the maximum penetration rate not exceed 1L/min m2Therefore, the particles of the cured material are not easy to compact, the argillization phenomenon is less, and the ore particles cannot be easily reduced, so that the humidity of the ore particles is high, the integrity of the ore particles can be ensured, and the permeation speed is high.
Preferably, in step 104, the degree of compaction of the matured material during column impregnation is less than or equal to 8%.
Specifically, the degree of compaction of the cured material is measured during column leaching to ensure that the degree of compaction is not more than 8% during the whole column leaching process, so that the curing material has less argillization, the ore particles cannot be easily reduced, the intact ore particles can be ensured, and the permeation speed is high.
The degree of compaction described in this example can be calculated according to the following formula:
degree of compaction ═ H1-H2)/H1×100％，
Wherein H1: height of ore particles before leaching, H2: the height of ore particles after leaching and before column discharge.
Preferably, in step 104, the time for column soaking the cured material is 30-90 days.
Specifically, the time for column leaching of the cured material is preferably 30-90 days, which is beneficial to H+Further contact with minerals, fully destroy the mineral structure, thereby improving the leaching rate of vanadium and ensuring a proper production period.
In summary, the method for extracting vanadium from low-grade stone coal vanadium ore provided by the embodiment of the invention effectively solves the problems that the requirement on the grade of raw ore is high, the stone coal vanadium ore needs to be ground to a certain fineness, and the aging leaching of the ground raw ore needs to be carried out under a certain temperature condition in the vanadium extraction process in the prior art, and is particularly suitable for leaching vanadium in low-grade stone coal vanadium ore.
It should be noted that the above-mentioned embodiments of the method are described as a series of actions for simplicity of description, but those skilled in the art should understand that the present invention is not limited by the described sequence of actions. Further, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred and that no particular act is required to implement the invention.
The invention is described in further detail below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example one
The raw ore is a certain stone coal vanadium ore in the United states, and V in the raw ore2O5The content of the vanadium is 0.32 wt%, and the occurrence state of the vanadium is different from that of sedimentary stone coal vanadium ore in China.
Crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 12 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing after 24 hours to obtain pelletized ore; wherein the mass ratio of concentrated sulfuric acid to crushed ore is 0.035: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of water to crushed ore is 0.02: 1, the adhesive is a high molecular polymer with the molecular weight of 3200 ten thousand;
curing the pellet ore for 5 days at normal temperature to obtain a cured material;
loading the cured material into a column, spraying dilute sulfuric acid to perform column leaching, controlling the concentration of the dilute sulfuric acid to be 15g/L, and controlling the initial spraying strength to be 0.15L/min m2The maximum penetration rate is 0.3L/min m2The degree of compaction is 7 percent, and the column leaching time is 90 days, so as to obtain vanadium-containing leaching solution;
the leaching solution containing vanadium is subjected to reduction, neutralization, extraction, back extraction, impurity removal, vanadium precipitation, calcination and other processes in sequence to obtain a refined vanadium product.
The first embodiment also compares the technical indexes of the stone coal vanadium ore treated by the method of the embodiment of the invention and the conventional strong acid leaching and low-temperature acid mixing curing-water leaching process. Wherein the process conditions of low-temperature acid mixing curing-water leaching are as follows: the particle size of the stone coal navajoite is less than 0.15mm, the curing temperature is 140 ℃, the curing time is 24 hours, the solid-to-solid ratio of the leaching solution of the cured material is 2:1, and the stone coal navajoite is stirred and leached for 1 hour at room temperature; the process conditions of the conventional strong acid leaching are as follows: the particle size of the stone coal vanadium ore is less than 0.15mm, the mass ratio of the stone coal vanadium ore to water is 1:1.2, the acid leaching temperature is 140 ℃, the leaching time is 24 hours, and specific indexes are shown in the following table 1.
TABLE 1 technical indexes of different vanadium extraction processes for certain stone coal vanadium ore in America
As can be seen from table 1, the method of the embodiment of the present invention can obtain a better vanadium leaching rate than the two common processes, i.e., the conventional strong acid leaching process and the low-temperature acid-mixing curing-water leaching process, and can also save the acid consumption. And the conventional process conditions of strong acid leaching and low-temperature sulfuric acid curing-water leaching are known, and both the conventional process conditions and the conventional process conditions need to ensure certain ore fineness and temperature to destroy the structure of the vanadium-containing mineral, so that the ore crushing and grinding cost and the energy consumption are increased.
Example two
The raw ore is a vanadium ore of a certain stone coal in Shanxi Shanyang, and V in the raw ore2O5The content of the mineral is 0.89 wt%, the raw ore mainly contains quartz, potash feldspar, sericite and the like, and in addition, the content of carbonate minerals such as calcite, dolomite and the like is high, so that the frequent overflow of a groove in the stirring and leaching process is caused, and the acid consumption is high.
Crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing after 24 hours to obtain pelletized ore; wherein the mass ratio of the concentrated sulfuric acid to the crushed ore is 0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of water to crushed ore is 0.07: 1, the adhesive is a high molecular polymer with the molecular weight of 3200 ten thousand;
curing the pellet ore for 5 days at normal temperature to obtain a cured material;
loading the cured material into a column, spraying dilute sulfuric acid to perform column leaching, controlling the concentration of the dilute sulfuric acid to be 10g/L, and controlling the initial spraying strength to be 0.35L/min m2The maximum penetration rate is 0.7L/min m2The degree of compaction is 8 percent, and the column leaching time is 30 days, so as to obtain vanadium-containing leaching solution;
the leaching solution containing vanadium is subjected to reduction, neutralization, extraction, back extraction, impurity removal, vanadium precipitation, calcination and other processes in sequence to obtain a refined vanadium product.
In the second embodiment, the technical indexes of the stone coal vanadium ore treated by the method of the embodiment of the invention and the conventional strong acid leaching and low-temperature acid mixing curing-water leaching process are also compared. Wherein the process conditions of low-temperature acid mixing curing-water leaching are as follows: the stone coal vanadium ore contains 60% of minerals with the particle size of less than 0.074mm, the curing temperature is 150 ℃, the curing time is 24 hours, and the mass ratio of the cured material to water is 1: 2, stirring and leaching for 1 hour at room temperature; the process conditions of the conventional strong acid leaching are as follows: the mineral content of the stone coal vanadium ore with the particle size of less than 0.074mm is 60%, the mass ratio of the stone coal vanadium ore to water is 1:1, the acid leaching temperature is 150 ℃, the leaching time is 24h, and specific indexes are shown in the following table 2.
Table 2 technical indexes of different vanadium extraction processes for certain stone coal vanadium ore in Shanxi Shanyang province
As can be seen from table 2, the method of the embodiment of the present invention can obtain a better vanadium leaching rate than the two common processes, i.e., the conventional strong acid leaching process and the low-temperature acid-mixing aging-water leaching process, and effectively reduce the acid consumption. The reason is that the acid-consuming minerals in the ore are high in content of calcite, dolomite and the like, so that the ore is not applicable to acid leaching after crushing, and the method provided by the embodiment of the invention is more applicable to vanadium extraction treatment of the stone coal vanadium ore.
EXAMPLE III
The raw ore is a stone coal vanadium ore in Shanxi Shannan, and V in the raw ore2O5The content of the vanadium is 0.78 wt%, the raw ore mainly contains carbon-silicon slate laminated slate and mudstone, the vanadium is closely related to the mudstone, and the mud content is highThe carbon content was 1.78%.
Crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing after 24 hours to obtain pelletized ore; wherein the mass ratio of the concentrated sulfuric acid to the crushed ore is 0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of water to crushed ore is 0.05: 1, the adhesive is a high molecular polymer with the molecular weight of 3200 ten thousand;
curing the pellet ore for 5 days at normal temperature to obtain a cured material;
loading the cured material into a column, spraying dilute sulfuric acid to perform column leaching, controlling the concentration of the dilute sulfuric acid to be 20g/L, and controlling the initial spraying strength to be 0.2L/min m2The maximum penetration rate is 0.5L/min m2The degree of compaction is 8 percent, and the column leaching time is 60 days, so as to obtain vanadium-containing leaching solution;
the leaching solution containing vanadium is subjected to reduction, neutralization, extraction, back extraction, impurity removal, vanadium precipitation, calcination and other processes in sequence to obtain a refined vanadium product.
In the third embodiment, the technical indexes of the stone coal vanadium ore treated by the method of the embodiment of the invention and the conventional strong acid leaching and low-temperature acid mixing curing-water leaching process are also compared. Wherein the process conditions of low-temperature acid mixing curing-water leaching are as follows: the particle size of the stone coal navajoite is less than 0.1mm, the curing temperature is 150 ℃, the curing time is 24h, and the mass ratio of the curing material to water is 1: 2, stirring and leaching for 2 hours at room temperature; the process conditions of the conventional strong acid leaching are as follows: the particle size of the stone coal vanadium ore is less than 0.1mm, the mass ratio of the stone coal vanadium ore to water is 1:1, the acid leaching temperature is 150 ℃, the leaching time is 24h, and specific indexes are shown in the following table 3.
Table 3 technical indexes of different vanadium extraction processes for certain stone coal vanadium ore in Shanxi province
As can be seen from table 3, the method of the embodiment of the present invention can obtain a better vanadium leaching rate than the two common processes of the conventional strong acid leaching and the low temperature acid-mixing aging-water leaching process, and the acid consumption is reduced by nearly one time. The reason is that the ore has extremely high mud content and contains 1.78% of carbon, so that the viscosity of ore pulp is increased by acid leaching after crushing, and the leaching process is influenced by carbon adsorption, so that the leaching rate of the ore of the type through conventional strong acid leaching and low-temperature acid mixing and curing-water leaching is not high.
Example four
The raw ore is a stone coal vanadium ore in the source of Shanxi Huayuan, and V in the raw ore2O5The content of the vanadium-containing mineral is 1.12 wt%, the raw ore mainly contains carbon-siliceous slate laminated slate and mudstone, and the vanadium-containing mineral is mainly sericite/illite and is secondly limonite, montmorillonite, kaolinite and schreyerite.
Crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 10 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing after 24 hours to obtain pelletized ore; wherein the mass ratio of the concentrated sulfuric acid to the crushed ore is 0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of water to crushed ore is 0.1: 1, the adhesive is a high molecular polymer with the molecular weight of 3200 ten thousand;
curing the pellet ore for 5 days at normal temperature to obtain a cured material;
loading the cured material into a column, spraying dilute sulfuric acid to perform column leaching, controlling the concentration of the dilute sulfuric acid to be 15g/L, and controlling the initial spraying strength to be 0.25L/min m2The maximum penetration rate is 0.45L/min m2The degree of compaction is 6 percent, and the column leaching time is 30 days, so as to obtain vanadium-containing leaching solution;
the leaching solution containing vanadium is subjected to reduction, neutralization, extraction, back extraction, impurity removal, vanadium precipitation, calcination and other processes in sequence to obtain a refined vanadium product.
In the fourth embodiment, the technical indexes of the stone coal vanadium ore treated by the method of the embodiment of the invention and the conventional strong acid leaching and low-temperature acid mixing curing-water leaching process are compared at the same time. Wherein the process conditions of low-temperature acid mixing curing-water leaching are as follows: the content of minerals with the grain size of less than 0.074mm in the stone coal vanadium ore is 53 percent, the curing temperature is 120 ℃, the curing time is 24 hours, and the mass of the cured material and water is 1: 2, stirring and leaching for 1 hour at room temperature; the process conditions of the conventional strong acid leaching are as follows: the mineral content of the stone coal vanadium ore with the particle size of less than 0.074mm is 53%, the mass ratio of the stone coal vanadium ore to water is 1:1, the acid leaching temperature is 100 ℃, the leaching time is 24h, and specific indexes are shown in the following table 4.
Table 4 technical indexes of different vanadium extraction processes of certain stone coal vanadium ore in Shaanxi Huayuan
As can be seen from table 4, the method of the present invention can obtain a similar vanadium leaching rate but lower acid consumption than the conventional two common processes, i.e., the strong acid leaching process and the low temperature acid-mixing aging-water leaching process. In consideration of the fact that the leaching period of the method is long, the method is not the most economical treatment process when being applied to high-grade stone coal vanadium ore, and is more suitable for vanadium extraction treatment of low-grade stone coal vanadium ore.
It can be seen from the above embodiments that the method provided by the embodiment of the invention has better adaptability to low-grade, high-calcium and carbon-containing stone coal vanadium ore, can obtain excellent technical indexes, and has the advantages of low ore crushing cost, low energy consumption, low acid consumption, convenience in production, short construction period and the like.
In the above embodiments of the present invention, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for extracting vanadium from low-grade stone coal vanadium ore is characterized by comprising the following steps:
crushing the stone coal vanadium ore to obtain crushed ore with the particle size of less than 15 mm;
adding concentrated sulfuric acid into the crushed ore, uniformly stirring, and adding an adhesive and water for pelletizing to obtain pelletized ore;
curing the pellet ore at normal temperature to obtain a cured material;
and filling the aged material into a column, spraying dilute sulfuric acid for column leaching to obtain vanadium-containing leaching solution.
2. The method according to claim 1, wherein in the step of obtaining crushed ore, V in the stone coal vanadium ore2O5The content of (B) is not less than 0.3 wt%.
3. The method according to claim 1 or 2, wherein in the step of obtaining the pellet ore, the mass ratio of the concentrated sulfuric acid to the crushed ore is 0.035-0.05: 1, the mass ratio of the adhesive to the crushed ore is 0.002: 1, the mass ratio of the water to the crushed ore is 0.05-0.1: 1.
4. the method according to claim 1 or 2, wherein in the step of obtaining the pellet ore, concentrated sulfuric acid is added into the crushed ore, and then the crushed ore is placed for 24 hours, and then the binder and water are added for carrying out the pellet.
5. A method according to claim 1 or 2, wherein the binder is a high molecular weight polymer having a molecular weight of greater than 3000 ten thousand.
6. The method as claimed in claim 1 or 2, wherein in the step of obtaining the ripened material, the time for the pellets to ripen at normal temperature is equal to or more than 72 hours.
7. The method according to claim 1 or 2, wherein in the step of obtaining the vanadium-containing leaching solution, the concentration of the dilute sulfuric acid is 10-20 g/L.
8. According to the claimsThe method of claim 1 or 2, wherein in the step of obtaining the vanadium-containing leachate, the initial spraying strength of the dilute sulfuric acid is not less than 0.1L/min m2The permeation speed of the dilute sulfuric acid is less than or equal to 1L/min-m2。
9. The method according to claim 1 or 2, wherein in the step of obtaining vanadium-containing leachate, the degree of compaction of the slaked material in column leaching is less than or equal to 8%.
10. The method according to claim 1 or 2, wherein in the step of obtaining the vanadium-containing leaching solution, the slaked material is subjected to column leaching for 30-90 days.
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