CN109112303B - Method for extracting vanadium from vanadium-containing stone coal mine - Google Patents
Method for extracting vanadium from vanadium-containing stone coal mine Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 126
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003245 coal Substances 0.000 title claims abstract description 82
- 239000004575 stone Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000012141 concentrate Substances 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007885 magnetic separation Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000009837 dry grinding Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 229910052952 pyrrhotite Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000006148 magnetic separator Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 2
- 239000002699 waste material Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011261 inert gas Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 17
- 238000002386 leaching Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052683 pyrite Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 5
- 239000011028 pyrite Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 229910052627 muscovite Inorganic materials 0.000 description 3
- 238000004094 preconcentration Methods 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IOXPXHVBWFDRGS-UHFFFAOYSA-N hept-6-enal Chemical compound C=CCCCCC=O IOXPXHVBWFDRGS-UHFFFAOYSA-N 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- -1 vanadium oxide ions Chemical class 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting vanadium from a vanadium-containing stone coal mine, which comprises the steps of crushing stone coal mine powder to be less than or equal to 50mm, screening the crushed stone coal mine into a plurality of size fractions, heating the stone coal mine with proper size fractions under the condition of vacuum or inert gas, recovering elemental sulfur, carrying out dry grinding and dry magnetic separation, and pre-enriching concentrate, cathode carbon, sulfuric acid and water of the vanadium-containing stone coal after magnetic separation according to the proportion of 100: 5-20: 20-40: 15-30, standing for a period of time, and then adding water for soaking. The method can effectively solve the problems of environmental pollution and low recovery rate of vanadium in the vanadium recovery process in the prior art, and can also solve the problem of disposal of waste electrolytic aluminum cathode carbon, and has the advantages of low production cost and high recovery rate.
Description
Technical Field
The invention relates to the field of vanadium extraction from vanadium-containing stone coal, in particular to a method for extracting vanadium from vanadium-containing stone coal ore.
Background
Vanadium, as a rare metal having an important strategic significance, is increasingly widely used in the fields of the aerospace industry, the atomic energy industry, the aerospace industry, the defense-oriented industry and the like, and is an indispensable important resource.
The vanadium-containing stone coal is an important vanadium ore resource unique in China, the reserves are extremely rich, vanadium exists in vanadium muscovite in the form of vanadium oxide, the vanadium muscovite is in the form of flaky or fan-shaped aggregate and coexists with flake stone coal, and the structure of the vanadium muscovite is very stable, so that the difficulty in extracting vanadium is increased. Furthermore, the vanadic stone-containing coal mines contain a large amount of impurities, such as pyrite, SiO2Etc. so that the ore V2O5The grade is low, and the vanadium ore is generally discarded along with tailings after the stone coal is recovered in many times, so that the huge waste of vanadium resources is caused.
During the production, casting and overhaul of the electrolytic cell of the primary aluminum, a large amount of waste cathode carbon blocks are generated, and about 20-30 kg of waste cathode carbon is generated for each ton of aluminum. The waste cathode carbon generally contains carbon, sodium fluoride, sodium hexafluoroaluminate, aluminum fluoride, calcium fluoride, aluminum oxide and other components, wherein the carbon accounts for about 50-70%, and the electrolyte fluoride accounts for about 50-30%. The treatment of the waste cathode carbon block mainly comprises a roasting method, a flotation method and a sulfuric acid decomposition method, and the methods can recover a part of electrolyte and carbon powder in the waste cathode carbon. However, the flotation method and the sulfuric acid decomposition method cannot remove the fluoride in the waste cathode carbon, and the fluoride entering the waste liquid is easy to cause secondary pollution; the carbon in the waste cathode carbon is recovered as fuel by adopting a roasting method, and the heat generated by combustion is difficult to be effectively utilized, so that a large amount of energy is wasted, and the requirement of strict temperature control in the roasting process cannot be met.
Existing method for enriching V from stone coal type vanadium ore2O5In the method, the wet method is generally adopted for extracting vanadium directly, but the method has the problems of high cost, easy three-waste pollution caused by the fact that pyrite in the vanadium ore is not treated, and low recovery rate of vanadium caused by the existence of the pyrite. Therefore, it is very important to find a method for extracting vanadium by using the waste cathode carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for extracting vanadium from a vanadium-containing stone coal mine. The method can effectively solve the problems of environmental pollution and low vanadium recovery rate in the vanadium recovery process in the existing vanadium extraction method.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a method for extracting vanadium from vanadium-containing stone coal ore comprises the following steps:
(1) will V2O5Crushing the stone coal vanadium ore with the content of 0.3-1.2% until the particle size is less than or equal to 50 mm;
(2) screening the crushed stone coal mine with coarse fraction in the step (1), and selectively pre-throwing the tail of the stone coal mine with the fraction of 2-50 mm;
(3) heating the stone coal ore remaining in the step (2) under the condition of vacuum or inert gas, wherein the heating temperature is 350-2350 ℃, the heating time is 1-6 min, and recovering sulfur simple substances in the heating process;
(4) carrying out dry grinding on the product obtained in the step (3) until all the product passes through a 100-mesh sieve;
(5) performing magnetic separation treatment on the product obtained in the step (4) to obtain pyrrhotite concentrate and vanadium-containing stone coal pre-enriched concentrate;
(6) and (3) pre-enriching concentrate of the vanadium-containing stone coal prepared in the step (5), cathode carbon, sulfuric acid and water according to the weight ratio of 100: 5-20: 30-40: 15-30, placing the mixture in a heat-insulating container for reaction for 7-14 days, and adding water into the heat-insulating container after the reaction is finished so that the solid-to-liquid ratio is 1-3: 1-3, then stirring for 2 hours, and finally filtering to obtain the vanadium-containing solution.
Further, V in the vanadium-containing stone coal2O50.3-1.2% of C, 15-30% of SiO2The content is 60-80%.
Further, in the step (2), stone coal mine with the grain size of +30mm is subjected to pre-tailing discarding.
Further, the step (3) is performed in a vacuum sintering furnace.
Further, the heating temperature in the step (3) is 600-700 ℃, and the heating time is 2-5 min.
Further, the equipment used for dry grinding in step (4) is a ball mill, a rod mill, a baseball mill or a pebble mill.
Further, a dry magnetic separator is adopted during the magnetic separation treatment in the step (5).
Further, in the step (6), the vanadium-containing stone coal pre-enriched concentrate, the cathode carbon, the sulfuric acid and the water are mixed according to the weight ratio of 100: 5-15: 30-35: 20-25, placing the mixture in a heat-insulating container for reaction for 7-10 days, and adding water into the heat-insulating container after the reaction is finished so that the solid-to-liquid ratio is 1-2: 1-2, then stirring for 2 hours, and finally filtering to obtain the vanadium-containing solution.
Further, in the step (6), the vanadium-containing stone coal pre-enriched concentrate, the cathode carbon, the sulfuric acid and the water are mixed according to the weight ratio of 100: 10: 30: 20, and placing the mixture in a container for reaction for 7 days; after the reaction is finished, adding water into the heat preservation container to ensure that the solid-to-liquid ratio is 1: 1, then stirring for 2 hours, and finally filtering to obtain the vanadium-containing solution.
Further, the sulfuric acid is 98% industrial sulfuric acid.
The invention has the beneficial effects that:
1. the method utilizes the different hardness of different minerals in the stone coal, combines the different occurrence states and contents of vanadium in different minerals, adopts a crushing mode to throw the tail in advance, throws the tail of the stone coal ore with the content less than or equal to 0.25 percent in advance, improves the content of vanadium pentoxide in the rest stone coal mine, facilitates the operation of the subsequent steps after preliminary enrichment work is carried out on the vanadium in the stone coal vanadium ore, saves the production cost and shortens the production time.
2. The cathode carbon generated in the electrolytic aluminum industry is skillfully applied to the field of vanadium extraction from stone coal, and because the fluorine in the waste cathode carbon is converted into hydrofluoric acid under an acidic condition in the leaching process, the hydrofluoric acid can be combined with silicon and aluminum in the vanadium-containing mica lattice to generate hexafluorosilicate and pentafluoroaluminate, the crystal structure of the vanadium-containing mica is completely destroyed, the vanadium-containing silicate mineral is dissolved, vanadium oxide ions are released into acid leaching liquid, the influence of chemical reaction on the vanadium leaching process is weakened, and the chemical control during the acid leaching process is changed into inner diffusion control from the chemical control during the participation of no fluoride, so that the vanadium leaching reaction is accelerated, and the leaching rate of vanadium is improved; the reaction raw materials are placed in a heat-preservation container, sulfuric acid releases heat when meeting water and provides heat for the reaction, and the heat-preservation container can control the temperature of the reaction materials within 80-150 ℃ without specially providing heat for the reaction; the waste cathode carbon is introduced into the field of vanadium extraction, so that the leaching rate of vanadium can be improved, the cost in the vanadium extraction process can be reduced, and the problem that the waste cathode carbon is difficult to recycle can be solved.
3. The invention utilizes the characteristic that the pyrite is converted into pyrrhotite and elemental sulfur at high temperature and in the inert gas atmosphere. Introducing the stone coal mineral subjected to tailing discarding in advance into a vacuum sintering furnace, heating the mineral in an inert gas atmosphere, converting pyrite into pyrrhotite and elemental sulfur, wherein the chemical reaction formula is FeS2The → Fe1-xS + xS reduces the content of sulfur in the stone coal vanadium ore, further enriches the vanadium in the stone coal vanadium ore, and simultaneously recovers the generated sulfur simple substance, thereby effectively avoiding the environmental pollution caused by the sulfur simple substance.
4. The dry-method ore grinding method is adopted, so that the process of volatilizing water after wet-method ore grinding is effectively avoided, the production steps are shortened, and the production time is greatly reduced; meanwhile, when dry grinding is adopted, because the vanadium is enriched in the process, the vanadium content in the stone coal mine is relatively increased, and when the stone coal mine is ground to a coarse particle size fraction, the next procedure can be carried out, so that the cost of grinding is reduced, the grinding time is shortened, and the production efficiency is improved.
5. The natural magnetism of the pyrrhotite is ingeniously utilized, the stone coal ore which is treated by the sintering furnace and ground by the dry method is sent to the dry magnetic separator for separation, and pyrrhotite concentrate and vanadium-containing stone coal concentrate are finally obtained.
6. The invention combines the processes of pre-tailing discarding, high-temperature vacuum treatment, dry ore grinding, dry magnetic separation and semi-wet vanadium extraction together for operation, and each step is mutually matched to finally realize the enrichment work of vanadium; the method has the advantages that firstly, compared with the conventional flotation pre-enrichment method, the method has the advantage of low cost, and the method solves the problem that the grade of low-grade vanadium-containing stone coal is difficult to improve under the condition of low cost; secondly, the problem that the environment is polluted by acid gas caused by stone coal fire desulphurization is solved, and the dual effects of quality improvement and impurity reduction of stone coal ores are realized; thirdly, a method combining pre-enrichment and high-temperature desulfurization is adopted, so that the recovery rate of vanadium is improved; and fourthly, the waste cathode carbon generated in the electrolytic aluminum industry is applied to the field of vanadium extraction from stone coal, so that the problem that the waste cathode carbon is difficult to recycle is successfully solved.
Detailed Description
Example 1
A high-efficiency desulfurization and preconcentration method of vanadium-containing stone coal comprises the following steps:
the stone coal mine in Sichuan has uneven appearance, dark brown color and V2O5The average content is about 0.353%, 68.86kg of ore is treated according to the method of the invention, crushed and then screened out with a dry screen in order to obtain coarse fractions of +50mm, 50-30 mm, 30-20 mm, 20-10 mm, 10 mm-2 mm and-2 mm, the weight of each fraction and V therein2O5The content and the distribution rate are detected, and the experimental results are shown in table 1. Heating the rest stone coal mine in a vacuum sintering furnace at 680-700 ℃ for 5min, and recovering sulfur simple substances in the heating process; will heat upPerforming dry grinding on the stone coal ore by using a ball mill until all the stone coal ore passes through a 100-mesh sieve; and then carrying out magnetic separation treatment by using a dry magnetic separator, wherein the magnetic separation adopts a rough scanning and a fine separation process to obtain pyrrhotite concentrate and vanadium-containing stone coal pre-enriched concentrate, and the magnetic separation result is counted and is shown in table 2.
TABLE 1 physical ore dressing and screening indexes of Szechwan stone coal and minerals
| Size fraction | Weight kg | Yield% | V2O5％ | Distribution ratio% |
| +50mm | 5.40 | 7.84 | 0.185 | 4.12 |
| 50～30mm | 10.00 | 14.52 | 0.232 | 9.56 |
| 30～20mm | 6.20 | 9.00 | 0.248 | 6.33 |
| 20～10mm | 9.66 | 14.03 | 0.328 | 13.05 |
| 10～2mm | 14.50 | 21.06 | 0.340 | 20.31 |
| ～2mm | 23.10 | 33.55 | 0.490 | 46.63 |
| Raw ore | 68.86 | 100.00 | 0.353 | 100.00 |
From Table 1, it is found that V is present in a rock coal mine having a size fraction of-20 mm2O5About 80% in stone coal mine with +20mm size fraction2O5The content is low, and the tailing can be used as tailings for tailing discarding.
TABLE 2 magnetic separation Experimental results
As shown in Table 2, the distribution rate of vanadium in the pre-enriched vanadium concentrate obtained by the method reaches 95.27%, and the distribution rate of sulfur in the sulfur concentrate reaches 79.77%, so that the aim of pre-enriching vanadium is fulfilled, and the sulfur concentrate is obtained.
Taking 1kg of the pre-enriched vanadium concentrate, mixing the pre-enriched vanadium concentrate with waste cathode carbon, 98% sulfuric acid and water according to the weight ratio of 100: 10: 30: 20 as experimental group; taking 1kg of the pre-enriched vanadium concentrate, and mixing the pre-enriched vanadium concentrate with concentrated sulfuric acid and water according to the weight ratio of 100: 30: 20 as a control group; respectively placing the experimental group and the control group in a heat-preservation container to react for 7 days; after the reaction is finished, adding water into the heat preservation container to ensure that the solid-to-liquid ratio is 1: 1 and then stirred for 2 hours. To V2O5The detection is carried out, and the specific results are shown in Table 3.
TABLE 3 results of the control and non-control experiments
As can be seen from Table 3, after the pre-enriched vanadium concentrate is treated by cathode carbon and 98% sulfuric acid, the grade of vanadium in the leaching residue is reduced to 0.05% from the original 0.46%, most vanadium elements are completely dissolved in the solution, and the leaching rate of vanadium is as high as 90.03%, so that the purpose of extracting vanadium with high efficiency is achieved.
Example 2
A high-efficiency desulfurization and preconcentration method of vanadium-containing stone coal comprises the following steps:
the stone coal mine in Sichuan has uneven appearance, dark brown color and V2O5The average content is about 1.2%, 70.12kg of ore is treated according to the method of the invention, crushed and then screened out with a dry screen in order to obtain coarse fractions of +50mm, 50-30 mm, 30-20 mm, 20-10 mm, 10 mm-2 mm and-2 mm, the weight of each fraction and V therein2O5The content and the distribution rate are detected, and the experimental result is shown in table 4. Heating the rest stone coal mine in a vacuum sintering furnace at 380-460 ℃ for 6min, and recovering sulfur elementary substances in the heating process; carrying out dry grinding on the heated stone coal ore by using a rod mill until all the stone coal ore passes through a 60-mesh sieve; then a dry magnetic separator is adopted for magnetic separation treatment, and the magnetic separation adopts oneRough scanning and a fine selection process are carried out to obtain pyrrhotite concentrate and vanadium-containing stone coal pre-enriched concentrate, the magnetic separation result is counted, and the specific result is shown in table 5.
TABLE 4 physical ore dressing, screening and ore dressing indexes for Szechwan stone coal and minerals
| Size fraction | Weight kg | Yield% | V2O5％ | Distribution ratio% |
| +50mm | 3.9 | 5.61 | 0.186 | 5.20 |
| 50～30mm | 5.4 | 7.70 | 0.239 | 8.59 |
| 30～20mm | 6.80 | 9.69 | 0.254 | 7.12 |
| 20～10mm | 11.23 | 16.01 | 1.998 | 14.55 |
| 10～2mm | 16.25 | 23.17 | 2.172 | 19.31 |
| ～2mm | 26.54 | 37.82 | 2.351 | 45.23 |
| Raw ore | 70.12 | 100.00 | 1.20 | 100.00 |
From Table 4, it can be seen that V is measured in a rock coal mine having a size fraction of-30 mm2O5About 86.7%, V in stone coal mine of +30mm size fraction2O5The content is low, and the tailing can be used as tailings for tailing discarding.
TABLE 5 magnetic separation Experimental results
As shown in Table 5, the distribution rate of vanadium in the pre-enriched vanadium concentrate obtained by the method of the invention reaches 95.26%, and the distribution rate of sulfur in the sulfur concentrate reaches 71.33%, so that the purpose of pre-enriching vanadium is realized, and the sulfur concentrate is obtained.
Taking 1kg of the pre-enriched vanadium concentrate, mixing the pre-enriched vanadium concentrate with waste cathode carbon, 98% sulfuric acid and water according to the weight ratio of 100: 15: 35: 25 as experimental group; taking 1kg of the pre-enriched vanadium concentrate, and mixing the pre-enriched vanadium concentrate with concentrated sulfuric acid and water according to the weight ratio of 100: 35: 25 as a control group; (ii) a After the reaction is finished, adding water into the heat preservation container to ensure that the solid-to-liquid ratio is 1: 2, and then stirred for 2 hours. To V2O5The detection is carried out, and the specific results are shown in Table 6.
TABLE 6 test results of control and non-control groups
As can be seen from Table 6, after the pre-enriched vanadium concentrate is treated by cathode carbon and 98% sulfuric acid, the grade of vanadium in the leaching residue is reduced to 0.32% from the original 2.45%, most vanadium elements are completely dissolved in the solution, and the leaching rate of vanadium is as high as 88.11%, so that the purpose of extracting vanadium with high efficiency is achieved.
Example 3
A high-efficiency desulfurization and preconcentration method of vanadium-containing stone coal comprises the following steps:
the stone coal mine in Sichuan has uneven appearance, dark brown color and V2O5The average content is about 0.895%, 66.54kg of ore is treated according to the method of the invention, crushed and then sieved by a dry sieve to obtain coarse fraction with the particle size of +50mm, 50-30 mm, 30-20 mm, 20-10 mm, 10 mm-2 mm and-2 mm, the weight of each fraction and V2O5The content and the distribution rate are detected, and the experimental result is shown in table 7. Heating the rest stone coal mine in a vacuum sintering furnace at 1750-1856 ℃ for 2min, and recovering sulfur simple substances in the heating process; carrying out dry grinding on the heated stone coal ore by using a ball mill until all the stone coal ore passes through a 100-mesh sieve; then a dry magnetic separator is adopted for magnetic separation treatment, the magnetic separation adopts a rough scanning and a fine selection process,and obtaining pyrrhotite concentrate and vanadium-containing stone coal pre-enriched concentrate, and counting the magnetic separation result, wherein the specific result is shown in a table 8.
TABLE 7 physical dressing, screening and mineral dressing indexes for Szechwan stone coal and minerals
| Size fraction | Weight kg | Yield% | V2O5％ | Distribution ratio% |
| +50mm | 3.3 | 4.95 | 0.194 | 4.12 |
| 50～30mm | 5.12 | 7.69 | 0.216 | 9.56 |
| 30～20mm | 7.91 | 11.89 | 0.249 | 6.33 |
| 20～10mm | 9.08 | 13.65 | 1.355 | 13.05 |
| 10～2mm | 14.61 | 21.96 | 1.495 | 20.31 |
| ～2mm | 26.52 | 39.85 | 1.860 | 46.63 |
| Raw ore | 66.54 | 100.00 | 0.895 | 100.00 |
From Table 7, it can be seen that V is measured in a rock coal mine having a size fraction of-30 mm2O5About 80% in stone coal mine with +30mm size fraction2O5The content is low, and the tailing can be used as tailings for tailing discarding.
TABLE 8 magnetic separation Experimental results
From table 8, it can be seen that the distribution rate of vanadium in the pre-enriched vanadium concentrate obtained by the method of the present invention reaches 95.02%, and the distribution rate of sulfur in the sulfur concentrate reaches 71.69%, so that the purpose of pre-enriching vanadium is achieved, and the sulfur concentrate is obtained.
Taking 1kg of the pre-enriched vanadium concentrate, mixing the pre-enriched vanadium concentrate with waste cathode carbon, 98% sulfuric acid and water according to the weight ratio of 100: 20: 40: 25 as experimental group; taking 1kg of the pre-enriched vanadium concentrate, and mixing the pre-enriched vanadium concentrate with concentrated sulfuric acid and water according to the weight ratio of 100: 40: 25 as a control group; respectively placing the experimental group and the control group in a heat-preservation container to soak for 10 days; after the reaction is finished, adding water into the heat preservation container to ensure that the solid-to-liquid ratio is 3: 1 and then stirred for 2 hours. To V2O5The results of the tests are shown in Table 9.
TABLE 9 results of the control and non-control experiments
From table 9, it is known that after the pre-enriched vanadium concentrate is treated by cathode carbon and 98% sulfuric acid, the grade of vanadium in the leaching residue is reduced to 0.22% from the original 1.86%, most vanadium elements are completely dissolved in the solution, the leaching rate of vanadium is as high as 87.81%, and the purpose of extracting vanadium with high efficiency is achieved.
Claims (6)
1. A method for extracting vanadium from vanadium-containing stone coal ore is characterized by comprising the following steps:
(1) crushing the stone coal vanadium ore until the particle size is less than or equal to 50 mm;
(2) screening the crushed stone coal mine with coarse fraction in the step (1), and selectively pre-throwing the tail of the stone coal mine with the fraction of 2-50 mm;
(3) heating the stone coal mine left in the step (2) under a vacuum condition, wherein the temperature is 600-700 ℃, the heating time is 2-5 min, and recovering sulfur simple substances in the heating process;
(4) carrying out dry grinding on the product obtained in the step (3) until all the product passes through a 100-mesh sieve;
(5) performing magnetic separation treatment on the product obtained in the step (4) to obtain pyrrhotite concentrate and vanadium-containing stone coal pre-enriched concentrate;
(6) and (3) pre-enriching concentrate of the vanadium-containing stone coal prepared in the step (5), cathode carbon, sulfuric acid and water according to the weight ratio of 100: 10: 30: 20, and placing the mixture in a container for reaction for 7 days; after the reaction is finished, adding water into the heat preservation container to ensure that the solid-to-liquid ratio is 1: 1, then stirring for 2 hours, and finally filtering to obtain the vanadium-containing solution.
2. The method of claim 1, wherein V is in the vanadium-containing stone coal2O50.3-1.2% of C, 15-30% of SiO2The content is 60-80%.
3. The method for extracting vanadium from vanadium-containing stone coal mine according to claim 1, wherein in the step (2), stone coal mine with the particle size fraction of +30mm is subjected to pre-tailing discarding.
4. The method for extracting vanadium from the vanadium-containing stone coal mine according to claim 1, wherein the equipment used for dry grinding in the step (4) is a ball mill, a rod mill, a baseball mill or a pebble mill.
5. The method for extracting vanadium from vanadium-containing stone coal mine as claimed in claim 1, wherein the magnetic separation in step (5) is performed by a dry magnetic separator.
6. A method of extracting vanadium from vanadium containing stone coal mine as claimed in claim 1 wherein the sulphuric acid is 98% industrial sulphuric acid.
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