CN111719054B - Oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore - Google Patents
Oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore Download PDFInfo
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- CN111719054B CN111719054B CN202010731734.2A CN202010731734A CN111719054B CN 111719054 B CN111719054 B CN 111719054B CN 202010731734 A CN202010731734 A CN 202010731734A CN 111719054 B CN111719054 B CN 111719054B
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y02P10/20—Recycling
Abstract
An oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore comprises the following steps: (1) crushing and grinding the stone coal vanadium ore to obtain fine ore; (2) conveying the mixture to a suspension decarburization roasting furnace for decarburization reaction; (3) the decarbonized materials are subjected to cyclone separation and then enter a suspension crystal breaking roasting furnace for crystal breaking oxidation reaction; (4) discharging the oxidized material after cyclone separation; (5) cooling to 150-200 ℃, mixing with acid, curing and leaching or directly leaching (6), filtering the leached materials to obtain V2O5Leaching liquor; (7) mixing the filter residue with a sodium hydroxide solution for secondary leaching, and filtering to obtain secondary filtrate; (8) adding hydrochloric acid into the secondary filtrate to generate white precipitate; filtering to obtain three filter residues, and drying to obtain the white carbon black. The method of the invention does not need to add sodium salt during roasting, and solves the problems of incomplete vanadium oxidation, low equipment treatment capacity, high operation cost and the like in the traditional process; the process flow is simple, the equipment and the system run stably, and the energy consumption and the cost of unit treatment capacity are low.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to an oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore.
Background
Vanadium is a rare high-melting-point nonferrous metal, is used as an alloy additive, can effectively improve the strength and toughness of the alloy, and is widely applied to the fields of steel production, aerospace, medical treatment and health, electronics, military industry and the like; 35% of vanadium consumption is closely related to national defense and military industry, and the strategic position of vanadium consumption cannot be replaced. Mineral resources for extracting vanadium mainly comprise vanadium titano-magnetite and stone coal, the prior art for extracting vanadium from stone coal has complex process flow, serious environmental pollution and high operation cost, and a large amount of waste residues after vanadium extraction are mostly stacked or filled in a wasteland by establishing a tailing pond, so secondary pollution and resource waste are easily caused; in addition, the acid leaching waste residue contains higher silicon. Therefore, if the vanadium can be efficiently and environmentally extracted and the silicon in the waste residue can be effectively utilized, the problems of insufficient vanadium supply, large land occupation of waste residue accumulation, secondary pollution and the like can be solved, and good economic benefit can be created.
Patent CN201910810064.0 discloses a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment acid leaching, which comprises mixing a leaching solution with the stone coal vanadium ore and an additive to carry out one-stage pretreatment to destroy the structure of vanadium-containing minerals in the stone coal, then carrying out two-stage pretreatment on the first-stage pretreated stone coal to carry out oxidative decomposition on the vanadium-containing minerals, and finally carrying out acid leaching to extract vanadium to obtain an acid leaching solution. The method can obviously improve the leaching rate of vanadium in the stone coal vanadium ore through two-stage pretreatment, but the method needs to add a large amount of additives, generates a large amount of waste residues which cannot be utilized, and has the problems of high cost, small treatment capacity, resource waste and the like. Patent CN201611083214.5 discloses a method for extracting vanadium by roasting vanadium-containing stone coal. Firstly, mixing vanadium-containing stone coal raw ore with a roasting additive, grinding, then preserving heat for 1-1.5 hours at 700-900 ℃ to obtain calcine, finally leaching out vanadium by dilute sulfuric acid, and using leaching slag as a cement admixture. In addition, decarburization proceeds simultaneously with the oxidation of vanadium, resulting in the interaction of the decarburization reaction with the oxidation reaction.
Disclosure of Invention
Aiming at the problems in the existing stone coal vanadium ore utilization technology, the invention provides an oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore, which comprises the steps of carrying out sectional treatment of decarburization and crystal breaking, then carrying out acid leaching and step-by-step filtration, improving the leaching rate of vanadium and simultaneously producing a byproduct of white carbon black.
The method of the invention is carried out according to the following steps:
1. crushing the stone coal vanadium ore to a particle size of less than or equal to 15mm, and then grinding the stone coal vanadium ore to a particle size of less than or equal to 1mm to obtain fine ore; the stoneThe coal vanadium ore contains V according to mass percentage2O5 0.6～1.2％；
2. Continuously conveying the fine ore to a suspension decarburization roasting furnace through a screw feeder; the bottom of the suspension decarburization roasting furnace is provided with a first burner and a gas inlet, the top of the suspension decarburization roasting furnace is provided with a feed inlet, and the upper part of the suspension decarburization roasting furnace is provided with a discharge outlet communicated with a first cyclone separator; introducing coal gas into the first burner, introducing oxygen and air into a gas inlet of the suspension decarburization roasting furnace, and starting flue gas generated by combustion of the first burner to enter the suspension decarburization roasting furnace; the fine ore entering the suspension decarburization roasting furnace is in a suspension state under the action of airflow and is heated to 750-850 ℃ by flue gas for decarburization reaction, and solid materials formed after decarburization reaction are decarburization materials and are discharged from a discharge hole of the suspension decarburization roasting furnace along with the flue gas;
3. the decarbonized materials discharged from the suspension decarbonization roasting furnace enter a first cyclone separator, are discharged from a discharge hole of the first cyclone separator after cyclone separation, and enter a suspension crystal breaking roasting furnace; the bottom of the suspension crystal breaking roasting furnace is provided with a second burner and a gas inlet, the top of the suspension crystal breaking roasting furnace is provided with a feed inlet, and the upper part of the suspension crystal breaking roasting furnace is provided with a discharge outlet communicated with a second cyclone separator; introducing coal gas into the second combustor, introducing oxygen and air into a gas inlet of the suspension crystal breaking roasting furnace, and starting flue gas generated by combustion of the second combustor to enter the suspension crystal breaking roasting furnace; the decarbonized materials entering the suspension crystal breaking roasting furnace are in a suspension state under the action of air flow, and are heated to 800-900 ℃ by flue gas to carry out crystal breaking oxidation reaction, solid materials formed after the crystal breaking oxidation reaction are oxidation materials and are discharged from a discharge hole of the suspension decarbonization roasting furnace along with the flue gas;
4. the oxidized materials discharged from the suspension decarburization roasting furnace enter a second cyclone separator, and are discharged from a discharge hole of the second cyclone separator after cyclone separation;
5. cooling the oxidized material to 150-200 ℃, and then carrying out acid mixing, curing and leaching or carrying out direct leaching; the acid mixing curing leaching is to place the oxidized material and a sulfuric acid solution with the mass concentration of 80-90% in a closed container, mix the oxidized material and the sulfuric acid solution under stirring for acid mixing curing, wherein the mass of the sulfuric acid solution is 40-45% of the total mass of the cooled material, add water to the cured material to leach the cured material, the amount of the water is 1-2 times of the total mass of the cured material, and the leaching time is 2-3 hours, so as to obtain a leached material; the direct leaching is to mix the oxidized material with a sulfuric acid solution with the mass concentration of 30-40%, then add an auxiliary leaching agent for leaching, wherein the mass of the sulfuric acid solution is 40-50% of the total mass of the oxidized material, the dosage of the auxiliary leaching agent is 3-5% of the total mass of the oxidized material, and the mixed leaching time is 6-8 hours, so as to obtain a leached material;
6. filtering the leached material to obtain filtrate and filter residue; the filtrate is used as V2O5Leaching liquor;
7. mixing the filter residue with a sodium hydroxide solution with the mass concentration of 20-25%, wherein the mixing ratio is that the mass ratio of the filter residue to the sodium hydroxide solution is 1 (4-5), and then carrying out secondary leaching to obtain a secondary leaching material; filtering the secondary leaching material to obtain secondary filtrate and secondary filter residue;
8. adding hydrochloric acid into the secondary filtrate to adjust the pH value to 7.5-9.5 to generate white precipitate; and then filtering to obtain three filtrates and three filter residues, and drying the three filter residues to remove water to prepare the white carbon black.
In the step 1, grinding until the grain diameter is less than or equal to 1mm, wherein the part with the grain diameter of 0.074mm accounts for 62-70% of the total mass, and obtaining fine ore.
In the step 2, the retention time of the fine ore in the suspension decarburization roasting furnace is 30-45 min; the volume flow ratio of the introduced oxygen to the introduced air is 1 (1-3).
In the step 2, the main reaction formula of the decarburization reaction is as follows:
C+nO2→2(1-n)CO22n-1 CO (1) and
4(CH)n+5n O2→4nCO2+2nH2O (2)。
in the step 3, the retention time of the decarburized material in the suspension crystal breaking roasting furnace is 60-120 min; the volume flow ratio of the introduced oxygen to the introduced air is 1 (3-8).
In the step 3, the main reaction formula of the crystal breaking oxidation reaction is as follows:
2V2O3+O2＝2V2O4 (3)、
2V2O4+O2＝2V2O5(4) and
4VO2+O2＝2V2O5 (5)。
in the step 4, when the oxidized material is cooled to 150-200 ℃, the oxidized material is placed into a cooler, the top of the cooler is provided with a feed inlet, the bottom of the cooler is provided with an air inlet communicated with an air compressor, the upper part of the cooler is provided with an air outlet, and the lower part of the cooler is provided with a discharge outlet; and blowing air into the cooler through an air compressor, carrying out countercurrent heat exchange on the oxidation material and the air, cooling to 150-200 ℃ to form a cooled oxidation material, discharging from the discharge hole, and carrying out step 5, wherein the temperature of the air subjected to heat exchange is 600-700 ℃, and the air is discharged from the air outlet.
In the step 5, the temperature of the material is controlled to be 130-140 ℃ during acid mixing and curing, and the time is 4-6 h.
In the step 5, the temperature of the material is controlled to be 80-90 ℃ when the leaching is directly carried out.
In the step 5, the leaching aid is CaF2。
In the above method, when the acid-mixed aging leaching is carried out in the step 5, V in the step 62O5V in the leach solution2O5The leaching rate is 83-88%; v of step 6 when step 5 is carried out for direct leaching2O5V in the leach solution2O5The leaching rate is 75-80%.
In the step 7, the main reaction formula in the secondary leaching is as follows:
SiO2+2NaOH＝Na2SiO3+H2O (6)。
in the step 8, the silica content of the white carbon black is 90-93% by mass.
In the above step 8, the main reaction formula for generating the white precipitate is:
Na2SiO3+2HCl＝H2SiO3+ NaCl (7) and
mH2SiO3＝mSiO3●nH2O↓+(m-n)H2O (8)。
in the step 8, the third filtrate is electrolyzed to prepare sodium hydroxide solution for recycling, and the main reaction formula of the sodium hydroxide solution prepared by electrolysis is as follows:
2NaCl+2H2O＝2NaOH+H2↑+Cl2and × (energization) (9).
Compared with the existing method for extracting vanadium from stone coal, the method adopts gas to carry out oxidation crystal breaking roasting on the stone coal vanadium ore, has high heat and mass transfer efficiency compared with static roasting, and solves the problems of incomplete vanadium oxidation, low equipment treatment capacity, high operation cost and the like in the static roasting process; sodium salt is not required to be added in the roasting process, the occurrence characteristic and valence state of vanadium are changed through roasting parameter regulation, and the oxidized crystal-breaking roasted product can adopt an acid-mixing curing-leaching process or a direct leaching process, so that the method has the advantages of strong adaptability, low operation cost, good environmental protection performance and the like; the 'decarbonization-crystal breaking oxidation' process of the coal-stone coal vanadium ore is subjected to sectional treatment by adopting a sectional roasting method, a product with uniform property is obtained in each stage, the influence of reducing carbon on vanadium oxidation is avoided, and meanwhile, decarbonization and crystal breaking oxidation can be carried out under the optimal conditions, so that the reaction efficiency is improved, the roasting time is shortened, and the accurate regulation and control of the stone coal vanadium in roasting are realized.
According to the invention, the vanadium extraction leaching residue is subjected to alkaline leaching treatment to prepare the white carbon black, so that the problems of large land occupation, secondary pollution and the like caused by accumulation of waste residues are solved; meanwhile, sodium hydroxide can be recycled by electrolyzing sodium chloride, heat energy is effectively utilized by heat exchange in the cooling process, energy is saved, the environment is protected, and the cost is reduced. The invention has the advantages of simple process flow, stable operation of equipment and a system, large treatment capacity, low energy consumption and cost of unit treatment capacity, easy control of product properties and easy realization of large-scale equipment.
Drawings
FIG. 1 is a schematic flow chart of the comprehensive utilization method of the stone coal vanadium ore by oxidation, crystal breaking and roasting in the embodiment of the invention.
Detailed Description
The mass concentration of the hydrochloric acid in the embodiment of the invention is 20-30%.
In the embodiment of the invention, the stone coal vanadium ore contains SiO in percentage by mass2 58～62％，Al2O3 7～8％，V2O50.6～1.2％，TFe 2～3％，CaO 2.5～3.5％，MgO 1～2％，Na2O 0.9～1.5％，C 10～13％。
In the embodiment of the invention, gas formed by cyclone separation of the first cyclone separator and the second cyclone separator enters the dust removal device.
The dust removal device in the embodiment of the invention is an electrostatic dust removal device.
The crushing in the embodiment of the invention adopts a jaw crusher.
The filtration in the embodiment of the invention adopts a plate-and-frame filter press.
The drying in the embodiment of the invention adopts a box type dryer.
The mass concentration of the hydrochloric acid in the embodiment of the invention is 20-30%.
In the embodiment of the invention, the air after heat exchange is introduced into the suspension decarburization roasting furnace.
The time of secondary leaching in the embodiment of the invention is 3.5-4.5 h; and the temperature during secondary leaching is 80-100 ℃.
Example 1
The flow is shown in figure 1;
crushing the stone coal vanadium ore to a particle size of less than or equal to 15mm, and then grinding the stone coal vanadium ore to a particle size of less than or equal to 1mm, wherein the part with the particle size of 0.074mm accounts for 62% of the total mass to obtain fine ore; the stone coal vanadium ore contains SiO in percentage by mass2 58.77％，Al2O3 7.2％，V2O51.05％，TFe 2～3％，CaO 3.22％，MgO 1.22％，Na2O 1.11％，C 12.5％；
Continuously conveying the fine ore to a suspension decarburization roasting furnace through a screw feeder; the bottom of the suspension decarburization furnace is provided with a first combustor and a gas inlet, the top of the suspension decarburization furnace is provided with a feed inlet, and the upper part of the suspension decarburization furnace is provided with a discharge outlet communicated with a first cyclone separator; introducing coal gas into the first combustor, introducing oxygen and air into a gas inlet of the suspension decarburization furnace, and starting flue gas generated by combustion of the first combustor to enter the suspension decarburization roasting furnace; the powder ore entering the suspension decarburization roasting furnace is in a suspension state under the action of airflow and is heated to 750 ℃ by flue gas for decarburization reaction, and solid materials formed after the decarburization reaction are decarburization materials and are discharged from a discharge hole of the suspension decarburization roasting furnace along with the flue gas; the retention time of the fine ore in the suspension decarburization roasting furnace is 45 min; the volume flow ratio of the introduced oxygen to the air is 1: 1;
the decarbonized materials discharged from the suspension decarbonization roasting furnace enter a first cyclone separator, are discharged from a discharge hole of the first cyclone separator after cyclone separation, and enter a suspension crystal breaking roasting furnace; the bottom of the suspension crystal breaking roasting furnace is provided with a second burner and a gas inlet, the top of the suspension crystal breaking roasting furnace is provided with a feed inlet, and the upper part of the suspension crystal breaking roasting furnace is provided with a discharge outlet communicated with a second cyclone separator; introducing coal gas into the second combustor, introducing oxygen and air into a gas inlet of the suspension crystal breaking roasting furnace, and starting flue gas generated by combustion of the second combustor to enter the suspension crystal breaking roasting furnace; the decarbonized material entering the suspension crystal breaking roasting furnace is in a suspension state under the action of air flow and is heated to 800 ℃ by flue gas to carry out crystal breaking oxidation reaction, and solid material formed after the crystal breaking oxidation reaction is oxidized material and is discharged from a discharge port of the suspension decarbonization roasting furnace along with the flue gas; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 120 min; the volume flow ratio of the introduced oxygen to the air is 1: 3;
the oxidized materials discharged from the suspension decarburization roasting furnace enter a second cyclone separator, and are discharged from a discharge hole of the second cyclone separator after cyclone separation;
putting the oxidized material into a cooler, wherein the top of the cooler is provided with a feed inlet, the bottom of the cooler is provided with an air inlet communicated with an air compressor, the upper part of the cooler is provided with an air outlet, and the lower part of the cooler is provided with a discharge outlet; air is blown into the cooler through the air compressor, the oxidation material and the air perform countercurrent heat exchange, the temperature is reduced to 150 ℃, the cooled oxidation material is discharged from the discharge hole, and simultaneously the air temperature after heat exchange is 600 ℃, and the oxidation material is discharged from the air outlet
Placing the cooled oxidized material and a sulfuric acid solution with the mass concentration of 80% in a closed container, mixing under stirring conditions for acid mixing and curing, wherein the mass of the sulfuric acid solution is 45% of the total mass of the cooled material, controlling the temperature of the material to be 130 ℃ during the acid mixing and curing, and the time is 6 hours, adding water into the cured material obtained after the acid mixing and curing, leaching the cured material, the water using amount of which is 1 time of the total mass of the cured material, and leaching for 3 hours to obtain a leached material;
filtering the leached material to obtain filtrate and filter residue; the filtrate is used as V2O5Leaching liquor; v2O5V in the leach solution2O5The leaching rate of (A) is 83%;
mixing the filter residue with a sodium hydroxide solution with the mass concentration of 20%, wherein the mixing ratio is 1:5 according to the mass ratio of the filter residue to the sodium hydroxide solution, and then carrying out secondary leaching to obtain a secondary leaching material; filtering the secondary leaching material to obtain secondary filtrate and secondary filter residue;
adding hydrochloric acid into the secondary filtrate to adjust the pH value to 9.5 to generate white precipitate; and then filtering to obtain third filtrate and third filter residue, and drying the third filter residue to remove water to prepare the white carbon black, wherein the mass content of the silicon dioxide is 90%.
Example 2
The method is the same as example 1, except that:
(1) the part with the grain diameter of 0.074mm in the fine ore accounts for 65 percent of the total mass; the stone coal vanadium ore contains SiO in percentage by mass260.2％，Al2O3 7.4％，V2O5 1.1％，TFe 2.55％，CaO 2.78％，MgO 1.43％，Na2O 1.25％，C 11.56％；
(2) The decarburization reaction temperature is 800 ℃; the retention time of the fine ore in the suspension decarburization roasting furnace is 40 min; the volume flow ratio of the introduced oxygen to the air is 1: 2;
(3) the temperature of the crystal breaking oxidation reaction is 850 ℃; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 90 min; the volume flow ratio of the introduced oxygen to the air is 1: 5;
(4) the oxidized material is cooled to 180 ℃ and discharged, and the air temperature after heat exchange is 650 ℃ and discharged;
(5) mixing the cooled oxidized material with a sulfuric acid solution with the mass concentration of 30%, adding an auxiliary leaching agent for leaching, controlling the temperature of the material to be 90 ℃, wherein the mass of the sulfuric acid solution is 50% of the total mass of the oxidized material, and the auxiliary leaching agent is CaF2The dosage of the leaching aid is 5 percent of the total mass of the oxidation materials, and the mixed leaching time is 6 hours to obtain leaching materials;
(6)V2O5v in the leach solution2O5The leaching rate of (A) is 80%;
(7) the mass concentration of the sodium hydroxide solution is 22%, and the mass ratio of the filter residue to the sodium hydroxide solution is 1: 4.5;
(8) adjusting the pH value to 7.5 to generate white precipitate; the mass content of silicon dioxide in the white carbon black is 92 percent.
Example 3
The method is the same as example 1, except that:
(1) the part with the grain diameter of 0.074mm in the fine ore accounts for 68 percent of the total mass; the stone coal vanadium ore contains SiO in percentage by mass261.43％，Al2O3 7.96％，V2O5 0.74％，TFe 2.97％，CaO 3.38％，MgO 1.28％，Na2O 0.95％，C10.36％；
(2) The decarburization reaction temperature is 850 ℃; the retention time of the fine ore in the suspension decarburization roasting furnace is 30 min; the volume flow ratio of the introduced oxygen to the air is 1: 3;
(3) the temperature of the crystal breaking oxidation reaction is 900 ℃; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 60 min; the volume flow ratio of the introduced oxygen to the air is 1: 8;
(4) the oxidized material is cooled to 200 ℃ and discharged, and the air temperature after heat exchange is 700 ℃ and discharged;
(5) the mass concentration of the sulfuric acid solution is 85 percent; the mass of the sulfuric acid solution is 43 percent of the total mass of the cooling material, the temperature of the material is controlled to be 135 ℃, and the time is 5 hours; when water is added for leaching, the using amount of water is 1.5 times of the total mass of the cured materials, and the leaching time is 2.5 hours;
(6)V2O5v in the leach solution2O5The leaching rate of (A) is 85%;
(7) the mass concentration of the sodium hydroxide solution is 23%, and the mass ratio of the filter residue to the sodium hydroxide solution is 1: 4;
(8) adjusting the pH value to 8 to generate white precipitate; the mass content of silicon dioxide in the white carbon black is 91 percent.
Example 4
The method is the same as example 1, except that:
(1) the part with the grain diameter of 0.074mm in the fine ore accounts for 66 percent of the total mass; the stone coal vanadium ore contains SiO in percentage by mass259.73％，Al2O3 7.66％，V2O5 0.79％，TFe 2.14％，CaO 2.96％，MgO 1.26％，Na2O 1.4％，C12.86％；
(2) The decarburization reaction temperature is 780 ℃; the retention time of the fine ore in the suspension decarburization roasting furnace is 35 min; the volume flow ratio of the introduced oxygen to the air is 1: 1.5;
(3) the temperature of the crystal breaking oxidation reaction is 820 ℃; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 100 min; the volume flow ratio of the introduced oxygen to the air is 1: 4;
(4) the oxidized material is cooled to 160 ℃ and discharged, and the air temperature after heat exchange is 630 ℃ and discharged;
(5) mixing the cooled oxidized material with a sulfuric acid solution with the mass concentration of 40%, adding an auxiliary leaching agent for leaching, controlling the temperature of the material to be 80 ℃, wherein the mass of the sulfuric acid solution is 40% of the total mass of the oxidized material, and the auxiliary leaching agent is CaF2The dosage of the leaching aid is 3 percent of the total mass of the oxidation materials, and the mixed leaching time is 8 hours to obtain leaching materials;
(6)V2O5v in the leach solution2O5The leaching rate of (A) is 80%;
(7) the mass concentration of the sodium hydroxide solution is 24%, and the mass ratio of the filter residue to the sodium hydroxide solution is 1: 4;
(8) adjusting the pH value to 8.5 to generate white precipitate; the silica content of the white carbon black is 93 percent.
Example 5
The method is the same as example 1, except that:
(1) the part with the grain diameter of 0.074mm in the fine ore accounts for 64 percent of the total mass; the stone coal vanadium ore contains SiO in percentage by mass258.89％，Al2O3 7.92％，V2O5 0.88％，TFe 2.87％，CaO 3.02％，MgO 1.79％，Na2O 1.13％，C11.4％；
(2) The decarburization reaction temperature is 820 ℃; the retention time of the fine ore in the suspension decarburization roasting furnace is 40 min; the volume flow ratio of the introduced oxygen to the air is 1: 2.5;
(3) the temperature of the crystal breaking oxidation reaction is 880 ℃; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 80 min; the volume flow ratio of the introduced oxygen to the air is 1: 6;
(4) the oxidized material is cooled to 190 ℃ and discharged, and the air temperature after heat exchange is 680 ℃ and discharged;
(5) the mass concentration of the sulfuric acid solution is 90 percent; the mass of the sulfuric acid solution is 40 percent of the total mass of the cooling material, the temperature of the material is controlled to be 140 ℃, and the time is 4 hours; when water is added for leaching, the using amount of water is 2 times of the total mass of the cured materials, and the leaching time is 2 hours;
(6)V2O5v in the leach solution2O5The leaching rate of (A) is 88%;
(7) the mass concentration of the sodium hydroxide solution is 25%, and the mass ratio of the filter residue to the sodium hydroxide solution is 1: 4;
(8) adjusting the pH value to 9 to generate white precipitate; the silica content of the white carbon black is 93 percent.
Claims (5)
1. An oxidation, crystal breaking and roasting comprehensive utilization method of stone coal vanadium ore is characterized by comprising the following steps:
(1) crushing the stone coal vanadium ore to a particle size of less than or equal to 15mm, and then grinding the stone coal vanadium ore to a particle size of less than or equal to 1mm, wherein the part with the particle size of 0.074mm accounts for 62-70% of the total mass to obtain fine ore; the stone coal vanadium ore contains V according to mass percentage2O5 0.6~1.2%；
(2) Continuously conveying the fine ore to a suspension decarburization roasting furnace through a screw feeder; the bottom of the suspension decarburization roasting furnace is provided with a first burner and a gas inlet, the top of the suspension decarburization roasting furnace is provided with a feed inlet, and the upper part of the suspension decarburization roasting furnace is provided with a discharge outlet communicated with a first cyclone separator; introducing coal gas into the first burner, introducing oxygen and air into a gas inlet of the suspension decarburization roasting furnace, and starting flue gas generated by combustion of the first burner to enter the suspension decarburization roasting furnace; the fine ore entering the suspension decarburization roasting furnace is in a suspension state under the action of airflow and is heated to 750-850 ℃ by flue gas for decarburization reaction, and solid materials formed after decarburization reaction are decarburization materials and are discharged from a discharge hole of the suspension decarburization roasting furnace along with the flue gas; the retention time of the fine ore in the suspension decarburization roasting furnace is 30-45 min; the volume flow ratio of the introduced oxygen to the air is 1 (1-3);
(3) the decarbonized materials discharged from the suspension decarbonization roasting furnace enter a first cyclone separator, are discharged from a discharge hole of the first cyclone separator after cyclone separation, and enter a suspension crystal breaking roasting furnace; the bottom of the suspension crystal breaking roasting furnace is provided with a second burner and a gas inlet, the top of the suspension crystal breaking roasting furnace is provided with a feed inlet, and the upper part of the suspension crystal breaking roasting furnace is provided with a discharge outlet communicated with a second cyclone separator; introducing coal gas into the second combustor, introducing oxygen and air into a gas inlet of the suspension crystal breaking roasting furnace, and starting flue gas generated by combustion of the second combustor to enter the suspension crystal breaking roasting furnace; the decarbonized materials entering the suspension crystal breaking roasting furnace are in a suspension state under the action of air flow, and are heated to 800-900 ℃ by flue gas to carry out crystal breaking oxidation reaction, solid materials formed after the crystal breaking oxidation reaction are oxidation materials and are discharged from a discharge hole of the suspension decarbonization roasting furnace along with the flue gas; the retention time of the decarburized materials in the suspension crystal breaking roasting furnace is 60-120 min; the volume flow ratio of the introduced oxygen to the air is 1 (3-8);
(4) the oxidized materials discharged from the suspension decarburization roasting furnace enter a second cyclone separator, and are discharged from a discharge hole of the second cyclone separator after cyclone separation;
(5) cooling the oxidized material to 150-200 ℃, and then carrying out acid mixing, curing and leaching or carrying out direct leaching; the acid mixing curing leaching is to place the oxidized material and a sulfuric acid solution with the mass concentration of 80-90% in a closed container, mix the oxidized material and the sulfuric acid solution under stirring for acid mixing curing, wherein the mass of the sulfuric acid solution is 40-45% of the total mass of the cooled material, add water to the cured material to leach the cured material, the amount of the water is 1-2 times of the total mass of the cured material, and the leaching time is 2-3 hours, so as to obtain a leached material; the direct leaching is to mix the oxidized material with a sulfuric acid solution with the mass concentration of 30-40%, and then add an auxiliary leaching agent to leach, wherein the auxiliary leaching agent is CaF2The mass of the sulfuric acid solution is the total mass of the oxidation material40-50% of the leaching aid, 3-5% of the total mass of the oxidation material, and mixing and leaching for 6-8 hours to obtain a leached material; controlling the temperature of the material to be 130-140 ℃ during acid mixing and curing, and keeping the time to be 4-6 h;
(6) filtering the leached material to obtain filtrate and filter residue; the filtrate is used as V2O5Leaching liquor;
(7) mixing the filter residue with a sodium hydroxide solution with the mass concentration of 20-25%, wherein the mixing ratio is that the mass ratio of the filter residue to the sodium hydroxide solution is 1 (4-5), and then carrying out secondary leaching to obtain a secondary leaching material; filtering the secondary leaching material to obtain secondary filtrate and secondary filter residue;
(8) adding hydrochloric acid into the secondary filtrate to adjust the pH value to 7.5-9.5 to generate white precipitate; and then filtering to obtain three filtrates and three filter residues, and drying the three filter residues to remove water to prepare the white carbon black.
2. The method for comprehensively utilizing the stone coal vanadium ore by oxidizing, breaking crystals and roasting according to claim 1, wherein in the step (2), the main reaction formula of the decarburization reaction is as follows:
C+nO2→2（1-n）CO22n-1 CO (1) and
4（CH）n+5 n O2→4nCO2+2nH2O （2）。
3. the method for comprehensively utilizing the stone coal vanadium ore by oxidizing, breaking crystals and roasting according to claim 1, wherein in the step (5), the temperature of the material is controlled to be 80-90 ℃ when the stone coal vanadium ore is directly leached.
4. The method for comprehensively utilizing the stone coal vanadium ore by oxidizing, breaking crystals and roasting as claimed in claim 1, wherein V in the step (6) is added when the step (5) is subjected to acid-mixed slaking leaching2O5V in the leach solution2O5The leaching rate is 83-88%; v of step (6) when step (5) is carried out by direct leaching2O5V in the leach solution2O5The leaching rate is 75-80%.
5. The method for comprehensively utilizing the stone coal vanadium ore by oxidizing, breaking crystals and roasting according to claim 1, wherein in the step (8), the silica content of the white carbon black is 90-93% by mass.
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| CN111876616B (en) * | 2020-07-27 | 2021-07-27 | 东北大学 | Stone coal navajoite oxidation, crystal breaking, roasting and vanadium extraction comprehensive utilization system |
| CN114134316B (en) * | 2021-10-29 | 2023-05-02 | 上海逢石科技有限公司 | System and method for extracting vanadium from stone coal vanadium ore through coarse-fine graded oxidation roasting |
| CN114111359A (en) * | 2021-10-29 | 2022-03-01 | 上海逢石科技有限公司 | Stone coal navajoite gradient oxidizing roasting vanadium extraction system and oxidizing roasting method |
| CN115747527A (en) * | 2022-11-22 | 2023-03-07 | 东北大学 | Vanadium extraction method of stone coal ore fluidized roasting-pressure leaching based on microwave heating |
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