CN109136551B - Method for extracting vanadium from high-calcium stone coal - Google Patents
Method for extracting vanadium from high-calcium stone coal Download PDFInfo
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- CN109136551B CN109136551B CN201811269333.9A CN201811269333A CN109136551B CN 109136551 B CN109136551 B CN 109136551B CN 201811269333 A CN201811269333 A CN 201811269333A CN 109136551 B CN109136551 B CN 109136551B
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- 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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- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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Abstract
The invention discloses a method for extracting vanadium from high-calcium stone coal, which comprises the following stepsThe following steps: directly conveying ore pulp obtained by wet grinding of raw ore in a ball mill into a closed tank, directly mixing the ore pulp with concentrated sulfuric acid, and curing the high-calcium stone coal by means of dilution heat and chemical reaction heat of the concentrated sulfuric acid; then adding water into a closed pool, blowing air and stirring to leach vanadium, and carrying out solid-liquid separation to obtain a blue vanadium leaching solution for preparing V2O5And (5) producing the product. The wet grinding method is adopted, the ore grinding is directly carried out without drying the ore, the ore grinding yield is high, the noise is low, and no dust exists; the slaked slag is in a slurry state, does not need to be crushed, and can be directly added with water to leach vanadium; the curing process adopts a heat-preserving and heat-insulating closed tank, which is beneficial to curing efficiency; the curing tank is combined with the leaching tower, so that the pollution of waste gas to the environment during curing is effectively prevented. The invention better solves the problems of complex process, high cost and environmental pollution in the prior art of vanadium extraction by concentrated sulfuric acid curing.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for extracting vanadium from high-calcium stone coal.
Background
The high calcium stone coal is one of vanadium-containing stone coal mines, the CaO content of the high calcium stone coal is usually more than 5 percent, and the high calcium stone coal is one of important vanadium extraction resources. However, the high-calcium stone coal is a kind of ore which is difficult to treat in the vanadium extraction industry because the high-calcium stone coal is rich in a large amount of dolomite, calcite and limestone minerals. If the traditional roasting-acid leaching method is adopted, calcium vanadate is generated in the leaching process, so that the leaching rate of vanadium is low, and in order to improve the leaching rate of vanadium, a plurality of patents disclose a flotation method for removing calcium-containing minerals. The disclosed Chinese invention patents (publication numbers CN103706465A, CN102274795A, CN103484667A and CN105032598A) provide a flotation beneficiation method for treating high-calcium stone coal, the technical scheme is a process of low-temperature roasting decarburization, medicament flotation decalcification, high-temperature roasting oxidation of low-valence vanadium and water leaching of vanadium, and the leaching rate of vanadium is 65-80%.
The technology of vanadium extraction by aging with concentrated sulfuric acid is a relatively environment-friendly method, and a plurality of methods are disclosedThe invention of the other aspect. However, the existing concentrated sulfuric acid curing method has many defects: for example, the problems of low ore grinding yield, high noise and flying dust exist in the process of crushing dry powder; when the dry powder and the concentrated sulfuric acid are mixed and stirred, a motor can be damaged, and when the belt is used for conveying the mixture, the concentrated sulfuric acid can easily damage the belt; SO released by concentrated sulfuric acid in reaction with minerals in open air or when stacked open2、CO2And HCl and other waste gases have hidden danger of environmental pollution; the cured slag is easy to agglomerate and become hard, and a crushing and scattering process is needed before vanadium is leached by water, so that the process is complicated. Therefore, there is a need for an improvement over the existing concentrated sulfuric acid aging process.
Disclosure of Invention
The invention aims to overcome the defects of the existing sulfuric acid curing method and solve the problems of low ore grinding yield, complicated process, easy damage of a stirrer, environmental pollution and the like in the existing technology for extracting vanadium from vanadium slag by curing.
In order to achieve the above object, the present invention provides a method for extracting vanadium from high-calcium stone coal, which employs a system comprising:
a closed pool, a sulfuric acid tank and a ball mill;
the closed pool is respectively connected with the sulfuric acid tank and the ball mill;
the method comprises the following steps:
step S1: inputting the high-calcium stone coal and water into a ball mill for wet grinding to obtain flowable ore pulp;
step S2: inputting the flowing ore pulp into a closed tank, and simultaneously inputting concentrated sulfuric acid into the closed tank through a sulfuric acid tank to perform self-heating curing on the high-calcium stone coal to obtain a rare-mud cured material;
step S3: adding water into the closed pool, and blowing air and stirring to leach vanadium to obtain a solid-liquid mixture;
step S4: and (4) extracting the solid-liquid mixture in the closed pool, and carrying out solid-liquid separation to obtain a vanadium leaching solution.
As a preferred embodiment of the present invention, the portion of the high-calcium rock coal briquette screened by the vibrating screen of less than 10cm is input into the ball mill before step S1 is performed.
As a preferred embodiment of the invention, the system further comprises a leaching tower and an alkali liquor pool, wherein the top of the closed pool is provided with an exhaust hole, and the leaching tower is connected with the exhaust hole through an exhaust pipe; the alkali liquor pool is connected with an atomizing pipe in the leaching tower through a high-pressure pump, and the atomizing pipe is used for spraying NaOH/H2O2Mixing an aqueous alkali solution; the method further comprises feeding the off-gas generated during the autothermal curing in step S2 to a leaching tower for absorption treatment.
In a preferred embodiment of the present invention, the content of CaO in the high-calcium stone coal is 8.14 wt% or more.
As a preferred embodiment of the present invention, V in the high-calcium stone coal2O5The mass fraction of (A) is 0.8-2.1%.
In a preferred embodiment of the present invention, the high-calcium stone coal has a lump size of less than 10cm and a water content of 3 to 9 wt%.
In a preferred embodiment of the present invention, in step S1, the amount of water added is 28 to 38 wt% based on the high-calcium stone coal. The water adding amount is larger than that after dry curing, and the water adding amount of the dry curing is 8-12 percent. The water is added during crushing, so that wet grinding can be completed, ore pulp can be formed at the same time, and the ore pulp flows in the mixture pipeline and is conveyed to the closed pool. One of the advantages is that the wet grinding can be carried out after the circulating water in the range is added, no dust and no noise are generated, and the yield is large. And secondly, the vanadium powder has fluidity, is automatically mixed with concentrated sulfuric acid in a closed tank, is in a sludge shape during curing, is also in a sludge shape after curing, does not agglomerate, and can be directly injected with water to leach vanadium in the tank.
In a preferred embodiment of the present invention, in step S2, the concentrated sulfuric acid is added in an amount of 38 to 45 wt% with respect to the high-calcium stone coal in step S1. The consumption of concentrated sulfuric acid is high, the concentrated sulfuric acid is favorable for dilution and heating of the concentrated sulfuric acid, the curing temperature can be kept at 135-165 ℃, the hypercalcite coal in the closed pool is cured by self-heating generated by dilution of the sulfuric acid, external heating is not performed in the whole curing process, and the unreacted concentrated sulfuric acid can also react with other valuable metal elements in the ore to generate sulfate for dissolution. If the addition amount of the sulfuric acid is less than 38 percent, the curing temperature is low, the high-calcium stone coal is not completely cured, and the vanadium leaching rate is low. If the addition amount of the sulfuric acid exceeds 50%, waste is caused, and the addition amount of sodium hydroxide is more required when the pH value is adjusted in the next step, so that the production cost is increased. Therefore, the amount of concentrated sulfuric acid added is most appropriate in the above range.
In a preferred embodiment of the present invention, in step S3, the amount of water added is 2 to 3L per 1kg of the high-calcium stone coal in step S1.
In a preferred embodiment of the present invention, in step S1, the wet grinding time is 10 to 20min, and the particle size of the obtained flowable ore pulp is 80 to 120 mesh. The wet grinding time ensures that the particle size of the obtained flowable ore pulp is 80-120 meshes. The yield of ore grinding by the ball mill is 25 tons/hour, and the wet ore grinding method eliminates noise and dust pollution and increases the ore grinding amount.
In a preferred embodiment of the present invention, in step S2, the aging time is 24-32 hours, the aging temperature is 135-165 ℃, and the pressure during the aging is 0.12-0.18 MPa. The above numerical range ensures the full reaction of the high calcium stone coal and the concentrated sulfuric acid, the high temperature is favorable for the chemical reaction of dissolving the metal vanadium by the sulfuric acid, the reaction is slow at low temperature, and the vanadium leaching rate is low. The temperature is too high, the pressure of the closed pool is too high, and the closed pool is cracked, and the pressure range is the most suitable pressure range through experimental verification of an inventor.
According to the invention, in step S2, specifically, when the high-calcium stone coal reaches 105-120 tons, stopping inputting ore pulp into the closed pool, and moving the mixed material pipeline to a second closed pool; and simultaneously closing the exhaust control valve, the feed inlet and the material pumping port, generating 135-165 ℃ high-temperature steam in the sealed pool, inserting a thermocouple to observe temperature change, connecting a pressure gauge to observe the pressure of the steam in the sealed pool, curing the high-calcium stone coal in the sealed pool to obtain a rare mud-shaped cured material, and directly inserting an air-blowing steel pipe to the bottom of the sealed pool to indicate that the cured material is free of agglomeration.
In a preferred embodiment of the present invention, in step S3, the time for air-blowing stirring is 1 to 2.5 hours, and the air-blowing stirring is performed by using an air compressor and the pressure is 6 to 10 MPa.
According to the invention, in step S4, the solid-liquid mixture in the closed tank is pumped out by an acid-proof pump, and is conveyed to a filter press for solid-liquid separation, and a vanadium leaching solution is collected, wherein the vanadium leaching solution is a deep blue solution and is a tetravalent vanadium solution, and the vanadium leaching solution is subjected to pH adjustment, hydrogen peroxide oxidation, resin adsorption, strong base elution, and ammonium chloride vanadium precipitation to obtain an ammonium metavanadate or vanadium pentoxide product.
As a preferred embodiment of the invention, the water adopted in the method is industrial circulating water, industrial water discharged from each production process is collected in a centralized manner, and the purified water is precipitated and filtered by lime, liquid caustic soda, sodium sulfide solution and the like, so that the circulating water avoids the outward discharge of waste water and causes environmental pollution.
In a preferred embodiment of the present invention, the closed tank is provided with a plurality of material inlets and a plurality of material outlets.
As a preferable embodiment of the invention, the sulfuric acid tank is connected with the closed tank through a sulfuric acid output pipe, and one end of the sulfuric acid output pipe, which is connected with the closed tank, directly extends into a feeding hole in the closed tank.
As a preferable embodiment of the invention, the ball mill is connected with the closed pool through a mixture conveying pipeline, and one end of the mixture pipeline, which is connected with the closed pool, directly extends into a feeding hole on the closed pool.
As a preferred embodiment of the present invention, the mix delivery pipe is a PVC pipe, a PE pipe, a steel pipe or a cast iron pipe.
As a preferable embodiment of the invention, the included angle between the bottom surface of the closed pool and the horizontal direction is 8-12 degrees.
In a preferred embodiment of the present invention, the exhaust pipe is provided with a plurality of exhaust control valves for controlling exhaust gas emission.
As a preferred embodiment of the present invention, an exhaust fan I is further disposed between the leaching tower and the exhaust pipe.
In a preferred embodiment of the present invention, the leaching tower is provided with an air outlet.
According to the invention, the spray pipe sprays NaOH/H2O2Mixed alkaline aqueous solution for absorbing SO in exhaust gas2、CO2HCl gas; more preferably, the NaOH/H2O2In mixed aqueous alkali, NaOH and H2O2The mass fractions of (A) and (B) are respectively 4-6% and 2-4%. As a preferred embodiment of the present invention, the spray pipe is more preferably multilayered.
As a preferred embodiment of the invention, the sulfuric acid output pipe is provided with a sulfuric acid metering pump.
In a preferred embodiment of the present invention, the sulfuric acid tank is further connected to a sulfuric acid inlet pipe.
As a preferred embodiment of the invention, the height of the sulfuric acid tank relative to the horizontal plane is higher than that of the closed pool. The ore pulp can automatically flow into the closed tank by utilizing the fall, so that the ore pulp generated by wet grinding does not need to be stirred and mixed with concentrated sulfuric acid.
In a preferred embodiment of the present invention, the ball mill is further connected to a hopper, and the hopper is provided with a circulating water inlet pipe.
In a preferred embodiment of the invention, a pulp control valve is arranged on the mixing material pipeline.
In a preferred embodiment of the present invention, the sulfuric acid output pipe is provided with a sulfuric acid control valve.
In a preferred embodiment of the present invention, the closed cell has a volume of 260 to 400m3The cement building is rectangular, and the inner walls of the cement building are subjected to acid-resistant treatment; the whole closed pool is 2.5-3.5 meters deep underground, the bottom of the pool is in a slope shape, the closed pool is inclined forwards by 8-12 degrees to collect solid-liquid mixture at the bottom, and the acid-resistant pump is favorable for completely pumping out the solid-liquid mixture.
As a preferred embodiment of the present invention, the feed inlet is located in the middle of the closed tank, and is used for inputting the ore pulp and concentrated sulfuric acid; the material pumping port is positioned at the front part of the closed tank and is used for adding water and pumping a solid-liquid mixture from the closed tank; the exhaust hole is positioned at the rear part of the closed pool and used for exhausting waste gas and redundant water vapor generated in the closed pool.
Compared with the prior curing technology, the invention has the advantages that:
according to the technical scheme provided by the invention, the raw material of the high-calcium stone coal is ground by a wet method, is not pre-dried and is directly input into a ball mill to be added with water for wet grinding, so that the high-calcium stone coal grinding method has the advantages of high wet grinding yield, low noise and no dust generation, and can provide a high-efficiency, noise-free and dust-pollution-free production environment; the ore pulp obtained by wet grinding is directly input into a closed tank through a PVC pipeline to be mixed with concentrated sulfuric acid, and the ore pulp and the concentrated sulfuric acid do not need to be stirred and mixed, so that the production process is simplified, and the cost is saved; and then, water is directly added into the closed pool, air blowing and stirring are carried out to leach vanadium, and the aged material is not required to be taken out, crushed and pulped to leach vanadium, so that the production process is greatly simplified, and the time is saved. The invention also particularly focuses on environmental protection and energy conservation, the provided closed tank has the functions of heat preservation and heat insulation and one-tank dual-purpose, external heating is not needed during curing, the curing temperature of the high-calcium stone coal can be maintained within 135-165 ℃ by heat energy generated by self curing reaction, the curing pressure is within 0.12-0.18 MP, and the maximum advantage is that SO generated in the curing process can be collected2、CO2And HCl and the like, and the waste gas is absorbed and treated by the leaching tower, so that zero emission of the waste gas is realized, and the requirement of environmental protection is met. The technical scheme provided by the invention is an environment-friendly aging vanadium extraction method, and solves the problems of complicated working procedures, high cost and waste gas pollution in the existing aging vanadium extraction technology.
Therefore, the method has the characteristics of high vanadium extraction efficiency and low pollution. Through determination, the leaching rate of vanadium reaches 92.26-99.61%, and the vanadium extraction of the high-calcium stone coal can be realized without pollution.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 shows a schematic flow diagram according to an embodiment of the invention.
Fig. 2 shows a schematic block diagram of a wet grinding-closed slaking vanadium extraction system employed according to one embodiment of the present invention.
Description of reference numerals: 1-sealing the pool; 2-a material pumping port; 3-a feed inlet; 4-air vent; 5-an exhaust pipe; 501-an exhaust control valve; 6-exhaust fan I; 7-a leaching tower; 701-a spray pipe; 8-air outlet; 9-a high pressure pump; 10-an alkaline solution pool; 11-sulfuric acid metering pump; 1101-sulfuric acid output pipe; 12-a sulfuric acid inlet pipe; 13-a sulfuric acid tank; 14-circulating water input pipe; 16-a hopper; 17-ball mill; 1701-conveying pipeline for mixed material; 301-a pulp control valve; 302-sulfuric acid control valve.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the embodiment of the invention, the flow schematic diagram of the method for extracting vanadium from high-calcium stone coal is shown in figure 1; the adopted vanadium extraction system is as follows:
as shown in fig. 2, an exhaust pipe 5 is arranged at the top of the closed pool 1, one end of the exhaust pipe 5 is connected with an exhaust hole 4, the other end of the exhaust pipe 5 is connected with an exhaust fan I6, an outlet of the exhaust fan I6 is connected with a leaching tower 7 (with the height of 6m) through a pipeline, so as to convey waste gas generated in the closed pool 1 to the leaching tower 7, a three-layer spray pipe 701 (only one layer of spray pipe 701 is shown in fig. 2 for convenient identification) is arranged in the leaching tower 7, and the spray pipe 701 is used for spraying NaOH/H2O2The mixed alkaline water solution is mixed with the alkaline water solution,for absorbing SO in exhaust gas2Gas, which is used for absorbing and purifying waste gas; the top of the leaching tower 7 is also provided with a gas outlet 8, and the purified gas is discharged through the gas outlet 8; wherein, the NaOH/H2O2In mixed aqueous alkali, NaOH and H2O2The mass fractions of (A) and (B) are respectively 5% and 3%. Arranged upstream of the washing tower 7 for storing the NaOH/H2O2An alkali liquor pool 10 for mixing the alkali liquor, wherein the alkali liquor in the alkali liquor pool 10 is delivered to a spray pipe 701 in the leaching tower 7 through a high-pressure pump 9 for spraying. The ball mill 17, the PVC pipeline 1701 and the sulfuric acid tank 13 are arranged at the upstream of the closed pool 1; one end of the mixture conveying pipeline 1701 is connected with the ball mill 17, and the other end of the mixture conveying pipeline 1701 directly extends into the feeding hole 3 of the closed pool; a sulfuric acid metering pump 11 is arranged at the outlet of the sulfuric acid tank 13, and a sulfuric acid output pipe 1101 directly extends into the feed inlet of the closed tank 1; when the amount of vanadium-containing stone coal in the closed pool 1 reaches 100-130 tons, closing the ore pulp control valve 301 and the exhaust control valve 501 to keep the closed pool 1 in a closed environment, thereby carrying out self-heating curing pretreatment, after the self-heating curing pretreatment is finished, opening the exhaust control valve 501 to pump out waste gas in the closed pool 1, conveying the waste gas to the leaching tower 7 for absorption treatment, when no waste gas exists, closing the exhaust control valve 501, opening the pumping hole 2 to add water into the closed pool 1, and blowing air to stir and leach vanadium; after leaching, the solid-liquid mixture is pumped out through the material pumping hole 2 for solid-liquid separation. In addition, the top of the closed pool 1 is closed by a cement prefabricated plate and is provided with a pumping hole 2, a feeding hole 3 and an exhaust hole 4.
Example 1
(1) Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O51.28 percent of CaO and 8.14 percent of CaO), adding 29.4 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/hour, and obtaining ore pulp with the granularity of 80 meshes.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 42 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool 1 reaches 105 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 165 ℃, the curing pressure is kept within the range of 0.18MP, and the curing time of the high-calcium stone coal in the closed pool 1 is kept at 32 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port 2 of the closed tank 1, adding 210 tons of circulating water, stirring for 2.5 hours by using air blowing of an air compressor to leach vanadium, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying the solid-liquid mixture to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of the leaching tower is 99.57 percent, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In the embodiment, the adding amount of the circulating water in the step (1) is changed to 30.5, 31.5, 33.6, 35.7, 37.8 and 39.9 tons and the leaching rate of vanadium is 93.76 to 99.43 percent while the steps (2), (3), (4) and (5) are kept unchanged, the content of CaO in the leaching solution is lower than 1.1 mu g/mL, and most of CaO is coexisted in the leaching slag as calcium sulfate slag.
Example 2
(1) Selecting the block height with water content of 8% and the block size smaller than 10cmCalcium stone coal (V)2O51.57 percent of CaO and 10.46 percent of CaO), and adding 41.8 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/hour, and the ore pulp with the granularity of 100 meshes is obtained.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 49.5 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud-shaped mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool 1 reaches 110 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 135 ℃, the curing pressure is kept within the range of 0.18MP, and the high-calcium stone coal is cured in the closed pool 1 for 24 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port of the closed tank 1, adding 275 tons of circulating water, stirring for 1.5 hours by using air blown by an air compressor to leach vanadium, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying the solid-liquid mixture to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of (2) is 97.14%, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In the embodiment, the adding amount of concentrated sulfuric acid in the step (2) is changed to 41.8, 42.9, 44, 45.1, 46.2, 47.3 and 48.4 tons while keeping the steps (1), (3), (4) and (5) unchanged, the leaching rate of vanadium is 93.26-98.89%, the content of CaO in the leaching solution is lower than 1.1 mu g/mL, and most of CaO exists in the leaching slag as calcium sulfate slag.
Example 3
(1) Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O51.18 percent of CaO and 9.47 percent of CaO), adding 38.5 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/h, and obtaining ore pulp with the granularity of 120 meshes.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 48.3 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud-shaped mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool reaches 115 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 150 ℃, the curing pressure is kept within the range of 0.18MP, and the high-calcium stone coal is cured in the closed pool 1 for 26 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port 2 of the closed tank 1, adding 250 tons of circulating water, stirring for 2.0 hours by using air blowing of an air compressor for leaching vanadium, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of the leaching tower is 96.41 percent, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In the embodiment, the slaking temperatures in the step (3) are changed to 135 ℃, 140, 145, 155, 160 and 165 ℃ and the leaching rate of vanadium is 93.56-99.52 percent while the steps (1), (2), (4) and (5) are kept unchanged, the leaching rate of vanadium is greatly influenced by the temperature, the content of CaO in the leachate is lower than 1.1 mu g/mL, and most of CaO exists in the leaching slag as calcium sulfate slag.
Example 4
(1) Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O50.96 percent of CaO and 10.74 percent of CaO, and adding 36 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/hour, and the ore pulp with the granularity of 80 meshes is obtained.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 48 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool 1 reaches 120 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 145 ℃, the curing pressure is kept within the range of 0.18MP, and the curing time of the high-calcium stone coal in the closed pool 1 is 28 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port 2 of the closed tank 1, adding 300 tons of circulating water, stirring for 2.4 hours by using air blowing of an air compressor for leaching vanadium, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of (3) is 95.48%, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In the embodiment, the slaking time in the step (3) is changed to 24, 25, 26, 27, 29, 30, 31 and 32 hours while the steps (1), (2), (4) and (5) are kept unchanged, the leaching rate of vanadium is 93.17-98.36%, the content of CaO in the leaching solution is lower than 1.1 mu g/mL, and most of CaO exists in the leaching slag as calcium sulfate slag.
Example 5
(1) Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O50.96 percent of CaO and 10.12 percent of CaO), adding 45 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/hour, and obtaining ore pulp with the granularity of 120 meshes.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 50 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool 1 reaches 125 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 165 ℃, the curing pressure is kept within the range of 0.18MP, and the high-calcium stone coal is cured in the closed pool 1 for 30 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port 2 of the closed tank 1, adding 275 tons of circulating water, stirring for 1.8 hours by using air blowing of an air compressor for vanadium leaching, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of the leaching tower is 96.48 percent, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In this example, the solid-to-liquid ratio in step (5) was changed to 1:2, 1: 2.1, 1: 2.4, 1: 2.6, 1: 2.8, 1: 3.0(kg/L), the leaching rate of the vanadium is 93.43-96.79%, and the solid-liquid ratio has little influence on the leaching rate. The content of CaO in the leaching solution is lower than 1.1 mu g/mL, and most of CaO exists in the leaching slag as calcium sulfate slag.
Example 6
(1) Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O50.96 percent of CaO and 9.78 percent of CaO, and adding 38.4 tons of circulating water into the ball mill 17 to carry out wet grinding for 10min, wherein the grinding yield of the high-calcium stone coal is 25 tons/hour, and the ore pulp with the granularity of 100 meshes is obtained.
(2) Opening the ore pulp control valve 301, enabling the ore pulp to continuously flow into the closed pool 1 through the PVC mixture conveying pipeline 1701, simultaneously opening the sulfuric acid control valve 302 to add 49.2 tons of concentrated sulfuric acid (approved by a sulfuric acid metering pump 11) into the closed pool 1, and automatically mixing the concentrated sulfuric acid and the concentrated sulfuric acid to obtain a thin mud-shaped mixture; when the ore pulp and the concentrated sulfuric acid are input, the material pumping port 2 of the closed tank 1 is closed, the exhaust control valve 501 and the exhaust fan I6 are opened, and the waste gas in the closed tank 1 is conveyed to the leaching tower 7 for absorption treatment.
(3) When the high-calcium stone coal in the closed pool 1 reaches 120 tons, the pumping hole 2 is continuously closed in the curing process, the ore pulp control valve 301 and the exhaust control valve 501 are closed at the same time, the operation of the exhaust fan I6 is stopped, the whole closed pool 1 is kept in a closed state, the curing temperature is kept at 145 ℃, the curing pressure is kept within the range of 0.18MP, and the high-calcium stone coal is cured in the closed pool 1 for 26 hours.
(4) When the mixture is cured, opening the exhaust control valve 501 and opening the exhaust fan I6, conveying gas generated in the stacking process of the mixture in the closed tank 1 into the leaching tower 7 for purification treatment, and discharging the purified gas through the gas outlet 8; when the exhaust gas is completely discharged, the suction port 2 is opened.
(5) After the gas purification treatment is finished, opening a material pumping port 2 of the closed tank 1, adding 200 tons of circulating water, stirring for 2.2 hours by using air blowing of an air compressor to leach vanadium, pumping a solid-liquid mixture from the material pumping port 2 by using an acid-resistant pump, and conveying the solid-liquid mixture to a plate-and-frame filter press for solid-liquid separation to obtain a blue vanadium leaching solution for preparing a vanadium product.
Method for measuring V in high-calcium stone coal and filter residue by adopting ferrous ammonium sulfate oxidation-reduction titration method2O5To obtain V in the high-calcium stone coal2O5The leaching rate of the leaching tower is 97.16%, and the gas purified by the leaching tower does not contain SO2、CO2And HCl and the like, and meets the gas emission standard.
In this example, the air-blowing stirring time in step (5) was varied to 1.5, 1.8, 2.1, 2.3, 2.4, 2.5h, keeping steps (1), (2), (3), (4) unchanged, and the vanadium leaching rate was 93.43-97.74%. The content of CaO in the leaching solution is lower than 1.1 mu g/mL, and most of CaO exists in the leaching slag as calcium sulfate slag.
Example 7
Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O51.57% CaO, 10.46%) 110 tons, 35 tons of circulating water and 40 tons of concentrated sulfuric acid.
The other procedures are the same as example 1, and the leaching rate of vanadium is 92.26-98.23%.
Example 8
Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O51.57% of CaO, 10.46% of CaO) 115 tons of circulating water, 40 tons of circulating water and 45 tons of concentrated sulfuric acid.
The other procedures are the same as example 1, and the leaching rate of vanadium is 94.13-99.15%.
Example 9
Selecting lump high calcium stone coal (V) with water content of 8% and lump size smaller than 10cm, and sieving with vibrating screen2O5The mass content of the mixed solution is 1.57 percent, the mass content of CaO is 10.46 percent) by 120 tons, circulating water by 35 tons and concentrated sulfuric acid by 45 tons.
The other procedures are the same as example 1, and the leaching rate of vanadium is 95.32-97.87%.
Comparative example 1
The operation method is the same as that of example 1, except that the high-calcium stone coal in the step (1) is dried at 100 ℃ for 2 days, and then is subjected to dry grinding, wherein the particle size of dry powder is 80 meshes, the yield of the ball mill is 5-6 tons/hour, the noise is 105 decibels, and the dust exceeds the standard. The comparative example 1 adds a drying procedure, so that the time is long, the grinding efficiency is low, the noise is high, and the dust pollution is serious.
Comparative example 2
Performing dry grinding according to comparative example 1, and mixing dry powder and water according to a mass ratio of 100: 12 stirring in a stirrer, adding 40% concentrated sulfuric acid by mass of dry powder, stirring in the stirrer, and stacking in a closed pool), wherein the leaching rate of vanadium is 89.78%. In this comparative example 2, the mixture was stirred in the stirrer, resulting in a halt in the middle of the stirrer for cleaning, and the working efficiency was poor. Compared with the examples 1-8, a stirring procedure is added.
Comparative example 3
The operation method is the same as that of the embodiment 1, except that in the step (2), when the ore pulp and the concentrated sulfuric acid are input, the suction port of the closed tank is opened, the exhaust control valve and the exhaust fan are closed, and the waste gas in the closed tank is not absorbed. And (4) keeping the whole closed tank in an open state in the step (3). In the comparative example 3, the aging temperature is 90-105 ℃, and the vanadium leaching rate is 69-76%; meanwhile, a large amount of white irritant smoke is diffused above the closed pool to pollute the environment and influence the whole production environment.
The embodiments and the comparative examples show that the method has the advantages of small investment scale, low production cost, simple industrial production, convenient operation, high vanadium leaching rate and the like. The method can also fully utilize the characteristics of heat insulation and preservation, waste gas collection and dual-purpose in one pool of the closed pool, build more accumulation pools, perform one-time curing treatment on thousands of tons of high-calcium stone coal, then add water and blow air to stir and leach, and continuously produce vanadium products according to a conventional method. The high-calcium stone coal raw ore adopted by the invention does not need mineral separation, decarburization and roasting treatment, avoids the disadvantages of overlarge energy consumption and waste gas pollution, and is an environment-friendly vanadium extraction method.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (1)
1. A method for extracting vanadium from high calcium stone coal, characterized in that the method employs a system comprising:
a closed pool (1), a sulfuric acid tank (13) and a ball mill (17);
the closed pool (1) is respectively connected with the sulfuric acid tank (13) and the ball mill (17);
the method comprises the following steps:
step S1: inputting the high-calcium stone coal and water into a ball mill (17) for wet grinding to obtain flowable ore pulp;
step S2: inputting the flowing ore pulp into a closed pool (1), inputting concentrated sulfuric acid into the closed pool (1) through a sulfuric acid tank (13), and carrying out self-heating curing on the high-calcium stone coal to obtain a rare-mud cured material;
step S3: adding water into the closed pool (1), and blowing air and stirring to leach vanadium to obtain a solid-liquid mixture;
step S4: extracting a solid-liquid mixture in the closed tank (1), and performing solid-liquid separation to obtain a vanadium leaching solution;
wherein in the step S1, the adding amount of water is 28-38 wt% relative to the high-calcium stone coal;
in the step S2, the adding amount of concentrated sulfuric acid is 38-45 wt% relative to the high-calcium stone coal in the step S1;
in the step S2, the curing time is 24-32 hours, the curing temperature is 135-165 ℃, and the pressure during curing is 0.12-0.18 MPa;
the system also comprises a leaching tower (7) and an alkali liquor tank (10), wherein the top of the closed tank (1) is provided with an exhaust hole (4), and the leaching tower (7) is connected with the exhaust hole (4) through an exhaust pipe (5); the alkali liquor pool (10) is connected with a spray pipe (701) in the leaching tower (7) through a high-pressure pump (9), and the spray pipe (701) is used for spraying NaOH/H2O2Mixing an aqueous alkali solution;
the method also comprises the steps of conveying the waste gas generated in the self-heating curing process in the step S2 to a leaching tower (7) for absorption treatment;
the content of CaO in the high-calcium stone coal is more than or equal to 8.14 wt%;
v in the high-calcium stone coal2O5The mass fraction of (A) is 0.8-2.1%;
in the step S3, the adding amount of water is 2-3L relative to 1kg of the high-calcium stone coal in the step S1;
in the step S1, the wet grinding time is 10-20 min, and the particle size of the obtained flowing ore pulp is 80-120 meshes;
in the step S3, the air blowing and stirring time is 1-2.5 h, an air compressor is used for air blowing and stirring, and the pressure is 6-10 MPa.
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