CN110564960A - Method for extracting vanadium by two-stage pretreatment acid leaching of stone coal vanadium ore - Google Patents
Method for extracting vanadium by two-stage pretreatment acid leaching of stone coal vanadium ore Download PDFInfo
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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
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Abstract
the invention relates to a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment acid leaching, which comprises the steps of mixing a leaching solution, 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 one-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 leaching solution is adopted to treat the stone coal vanadium ore in the first-stage pretreatment process, so that the acid consumption in the treatment process is reduced, the leaching rate of vanadium in the stone coal vanadium ore is obviously improved through two-stage pretreatment, and further, vanadium in stone coal vanadium ores with different properties can be leached through two-stage pretreatment, so that the method has the advantages of high vanadium leaching rate, low acid consumption, good process adaptability, strong continuity and the like.
Description
Technical Field
The invention relates to the technical field of vanadium extraction from stone coal vanadium ore, in particular to a two-stage pretreatment acid leaching vanadium extraction method for stone coal vanadium ore.
Background
the stone coal is a black carbonaceous shale, is an early ancient coal, is formed by piling up the dead bacteria and algae in shallow sea under the reducing condition, usually contains vanadium besides siliceous matter, is one of the main raw materials for extracting vanadium, and also contains various associated elements such as aluminum, potassium, iron, calcium, magnesium, molybdenum, nickel, cobalt, copper, titanium, chromium, uranium, selenium and the like. The stone coal vanadium ore accounts for 30 percent of the total production raw materials of the vanadium products in China, and is an important production raw material of the vanadium products in China.
the existing method for extracting vanadium from stone coal vanadium ore mainly comprises two main types: roasting and acid leaching. For example, patents CN101363084A, CN103215440A, CN104726694A, CN106244796A, CN101215647A, CN104711437A, CN101857915A, CN102766762A and CN102778121A all adopt roasting mode to make vanadium extraction treatment on stone coal. However, because the content of carbon, sulfur, nitrogen and other elements in the stone coal is too high, the fluctuation of the organic element components can cause the instability of the roasting process, so that the vanadium extraction process by the roasting method has serious pollution and low vanadium recovery rate.
In order to solve the problem of the roasting method, an acid leaching process is mostly adopted at present, when most of vanadium in stone coal raw ore exists in a higher valence state, a direct acid leaching method can achieve a better vanadium extraction effect, for example, a direct acid leaching method is adopted for Dazilin (research for improving vanadium leaching rate in stone coal vanadium ore, nonferrous metals (ore dressing part), 2010(4):29-31.) aiming at the village vanadium ore in Wuzhou mining industry limited company in Shanxi, because the ore area mainly contains tetravalent vanadium, the vanadium is easy to extract, and the vanadium leaching rate is more than 80%. However, for refractory stone coal with high content of low-valence vanadium, the direct acid leaching effect is not good, the acid dosage needs to be increased and the acid leaching time needs to be prolonged, so as to avoid the problem that the acid leaching is increased by adding a fluoride additive to destroy the vanadium mica structure, for example, wuhaiying eagle (research on the influence of a fluorine-containing leaching aid on sulfuric acid leaching and vanadium extraction of vanadium ore, ore smelting process, 2010,30(2):83-84,88.) adopts the addition of a fluorine leaching aid to perform acid leaching on vanadium, the leaching rate is increased by 13% compared with the leaching rate of vanadium by direct acid leaching, but fluoride is toxic, and fluorine-containing wastewater is difficult to treat.
In order to solve the above problems, there are some documents which adopt methods of vanadium extraction such as external field assisted acid leaching, sulfuric acid aging-water leaching/acid leaching and the like. CN101550493A proposes a method for rapidly leaching vanadium in stone coal vanadium ore with the assistance of microwave, which adopts 5-20% sulfuric acid, 0.3GHz-300GHz microwave, 100 ℃ and 1-10:1 liquid-solid ratio to react for 100min, and the leaching rate of vanadium is improved by 9% compared with that of water bath heating. CN103160696A proposes a method for extracting vanadium from vanadium-containing stone coal by microwave heating, which comprises the steps of uniformly wetting vanadium-containing stone coal particles with sulfuric acid solution, carrying out microwave heating after wetting, wherein the heating temperature is 100-180 ℃, the heating time is 3-30min, then adding the heated vanadium-containing stone coal into water, carrying out stirring leaching at 25-100 ℃, and then carrying out liquid-solid separation to obtain vanadium-containing leachate.
The method has the problems of large sulfuric acid consumption and poor process applicability, and provides a method for reducing leaching acid consumption and impurity leaching rate of high-acid-consumption vanadium ore in order to reduce the sulfuric acid consumption CN 104531989A. The method has the advantages that during the roasting process by adding calcium, acid-consuming minerals in the ores are decomposed and phase-changed at high temperature and are converted into minerals which are difficult to react with dilute sulfuric acid, and the aim of reducing acid is achieved during leaching. However, the method is still a roasting process, and still has the problems of serious pollution, low vanadium recovery rate and the like in the vanadium extraction process. CN103421964A proposes a method for leaching vanadium from vanadium-containing stone coal, which comprises the steps of crushing and ball-milling the stone coal, leaching the stone coal with a second-stage acid leaching solution according to a liquid-solid ratio (2.5-5):1 at 80-100 ℃ for 1-4h, using a first-stage leaching solution for subsequent enrichment of vanadium, adding 1-7% of CaF into a first-stage leaching residue in 10-25% of sulfuric acid solution according to a liquid-solid ratio (0.8-2):12Soaking at 80-100 deg.C for 4-8 hr, and two-stage soakingThe acid leaching residue is the final residue. The method has the advantages of low acid consumption and proper pH value of the acid leaching solution, but the method has the problems that a toxic fluoride additive is added, the method can only treat the stone coal with high oxide content, the solid-to-solid ratio of the two sections of acid leaching solutions is different, the solid-to-solid ratio of the one section of acid leaching solution is large, and the solid-to-solid ratio of the two section of acid leaching solution is small, so that the two sections of acid leaching solution in the one section of acid leaching process is insufficient to treat the stone coal, and the continuous operation of the vanadium extraction production of the stone.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for extracting vanadium by two-stage pretreatment acid leaching of stone coal vanadium ore, which has the advantages of high vanadium leaching rate, low acid consumption, good process adaptability, strong continuity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
The invention provides a method for extracting vanadium by two-stage pretreatment and acid leaching of stone coal vanadium ore, which comprises the following steps:
(1) Adding stone coal vanadium ore and an additive into the leaching solution to carry out primary pretreatment, and carrying out solid-liquid separation to obtain primary pretreatment solution and primary pretreated stone coal;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid, and performing second-stage pretreatment to obtain second-stage pretreated stone coal;
(3) And (3) performing acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, performing solid-liquid separation to obtain acid leaching solution and acid leaching slag, wherein the acid leaching solution is used as the leaching solution of the first-stage pretreatment in the step (1).
The invention provides a method for extracting vanadium from acid leaching solution for two-stage pretreatment of stone coal vanadium ore, which comprises the steps of mixing leaching solution with stone coal vanadium ore and additives for one-stage pretreatment to destroy the structure of the stone coal, then carrying out two-stage pretreatment on the one-stage pretreated stone coal to carry out oxidative decomposition on the vanadium-containing mineral, and finally carrying out acid leaching and vanadium extraction to obtain the acid leaching solution.
As a preferable technical scheme of the invention, the stone coal vanadium ore in the step (1) is crushed and ball-milled until the granularity is-40 meshes.
As a preferred embodiment of the present invention, the additive in step (1) is one or a combination of at least two of iron oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric carbonate, ferrous carbonate, basic ferric carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, basic magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, magnesite, siderite or dolomite, and typical but non-limiting combinations include a combination of iron oxide and ferrous oxide, a combination of iron hydroxide and ferrous hydroxide, a combination of iron carbonate and ferrous carbonate, a combination of basic iron carbonate and magnesium oxide, a combination of magnesium hydroxide and magnesium carbonate, a combination of magnesium bicarbonate and basic magnesium carbonate, a combination of calcium oxide and calcium hydroxide, a combination of calcium carbonate and magnesite, a combination of siderite and dolomite, and the like, but is not limited thereto and for the sake of brevity, the present invention is not exhaustive.
Preferably, the pH of the first stage pretreatment solution is 1 to 4, such as 1, 1.2, 1.5, 1.8, 2, 2.3, 2.5, 2.7, 3, 3.5, or 4, but is not limited to the recited values, and other values not recited within this range are equally applicable, preferably 1.5 to 3.
The invention can add a small amount of additives aiming at the stone coal with high content of calcium oxide, magnesium oxide, ferric oxide, calcite, dolomite and the like, and can add a certain amount of additives aiming at the stone coal with low content of calcium oxide, magnesium oxide, ferric oxide, calcite, dolomite and the like to carry out primary pretreatment. Therefore, the process can be suitable for the stone coal with different metal oxide contents, and the subsequent vanadium liquid purification and enrichment operation can be directly carried out on the first-stage pretreatment liquid through the action of the leaching liquid, the stone coal and the additive, so that the consumption of the neutralizing agent in the purification and enrichment process is reduced, and the process continuity is high.
in a preferred embodiment of the present invention, the liquid-solid ratio of the leachate to the stone coal vanadium ore in the first pretreatment in step (1) is (0.1 to 5):1, for example, 0.1:1, 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1 or 5:1, but not limited to the values listed, and other values not listed within this range are also applicable, and preferably (0.25 to 2.5): 1.
Preferably, the temperature of the first pretreatment in step (1) is 25 to 100 ℃, such as 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other non-recited values within this range are equally applicable, preferably 30 to 80 ℃.
Preferably, the period of the pretreatment in step (1) is 10-300min, such as 10min, 20min, 30min, 45min, 60min, 75min, 90min, 100min, 120min, 150min, 180min, 200min, 210min, 240min or 300min, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 30-180 min.
Preferably, the primary pretreatment solution of the step (1) is used for purifying and enriching vanadium.
According to the invention, the leaching solution and the additive are adopted to treat the stone coal vanadium ore in the first-stage pretreatment, so that the acid consumption oxide in the stone coal is consumed, the acid consumption in the technological process is reduced, the vanadium-containing mineral structure of the stone coal can be primarily destroyed under appropriate conditions, and the release of vanadium in the subsequent second-stage pretreatment is facilitated.
as a preferable technical scheme of the invention, the concentration of the sulfuric acid in the step (2) is more than or equal to 95 percent.
Preferably, the mass ratio of the stone coal to the sulfuric acid in the primary pretreatment is 1 (0.1-0.5), such as 1:0.1, 1:0.125, 1:0.15, 1:0.2, 1:0.225, 1:0.25, 1:0.3, 1:0.35, 1:0.40, 1:0.45 or 1:0.5, but not limited to the recited values, and other values within the range are equally applicable, preferably 1 (0.15-0.3).
In a preferred embodiment of the present invention, the temperature of the two-stage pretreatment in step (2) is 80 to 320 ℃, for example, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 125 ℃, 150 ℃, 165 ℃, 180 ℃, 200 ℃, 225 ℃, 250 ℃, 260 ℃, 270 ℃, 290 ℃, 300 ℃, 310 ℃ or 320 ℃, but is not limited to the recited values, and other values not recited in the above range are also applicable, preferably 100 to 300 ℃.
Preferably, the time of the two-stage pretreatment in step (2) is 5-200min, such as 5min, 10min, 15min, 20min, 30min, 45min, 60min, 75min, 90min, 100min, 120min, 135min, 150min, 165min, 180min or 200min, but is not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 20-120 min.
As a preferred technical scheme of the invention, acid mist is generated in the treatment process of the secondary pretreatment, and preferably, the acid mist is absorbed by water.
in the invention, the structure of the vanadium-containing mineral in the stone coal is primarily destroyed after the stone coal vanadium ore is subjected to primary pretreatment, and during secondary pretreatment, acid and air react with the vanadium-containing aluminosilicate mineral more rapidly, so that the mineral is completely decomposed and low-valence vanadium in the mineral is completely oxidized, thereby improving the leaching rate of vanadium. Meanwhile, the first-stage pretreatment stone coal can carry part of the first-stage pretreatment liquid, so that the acid consumption of the second-stage pretreatment is reduced.
Acid mist generated in the secondary pretreatment process is absorbed by water and then used for acid leaching vanadium in the step (3), namely, the process basically does not generate waste gas, and the pollution of the process to the environment is reduced.
As a preferable technical scheme of the invention, the acid solution used in the acid leaching vanadium in the step (3) is a water absorption solution of the acid mist in the secondary pretreatment in the step (2).
Preferably, the liquid-solid ratio of the acid solution to the second-stage pretreated stone coal in the step (3) is (0.1-5):1, for example, 0.1:1, 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1 or 5:1, but not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable, preferably (0.25-2.5): 1.
The solid in the liquid-solid ratio in the first-stage pretreatment and acid leaching vanadium extraction processes is converted according to the stone coal raw ore, and the conversion reason is that the leaching liquid amount is matched with the stone coal vanadium ore amount in the first-stage pretreatment, so that the vanadium extraction production of the stone coal vanadium ore can be continuously operated.
As a preferred embodiment of the present invention, the temperature of the acid leaching of vanadium in step (3) is 25 to 100 ℃, for example, 25 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the above range are also applicable, preferably 30 to 80 ℃.
preferably, the time for acid leaching vanadium in step (3) is 0.1-6h, such as 0.1h, 0.25h, 0.5h, 1h, 1.5h, 2h, 3h, 4h, 5h or 6h, but not limited to the recited values, and other values in the range are also applicable, preferably 0.25-3 h.
The common types of the stone coal vanadium ore are weathered type and primary type, wherein primary type stone coal vanadium is difficult to extract in mica, and most of stone coal in China belongs to the mica type refractory stone coal. Different mica type refractory stone coals comprise high-calcium mica type stone coal, high-iron mica type stone coal and high-calcium high-iron mica type stone coal according to the content difference of minerals such as iron, calcium, magnesium and the like in the stone coal, and some stone coals have lower vanadium content and are low-vanadium mica type stone coals.
The method reduces the content of acid-consuming substances of the stone coal vanadium ore through a first-stage pretreatment, and primarily destroys the vanadium-containing mineral structure; through two-stage pretreatment and acid leaching vanadium extraction processes, vanadium-containing minerals are completely destroyed, and vanadium in the stone coal vanadium ore is thoroughly leached. Therefore, the invention is suitable for high acid consumption, difficult extraction and other various types of stone coal vanadium ores.
as a preferred technical scheme of the invention, the method comprises the following steps:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio (0.1-5):1, adding an additive to perform first-stage pretreatment at a temperature of 25-100 ℃ for 10-300min, and performing solid-liquid separation to obtain first-stage pretreated stone coal and first-stage pretreatment liquid with a pH value of 1-4, wherein the first-stage pretreatment liquid is used for purifying and enriching vanadium; wherein the additive is any one or the combination of at least two of ferric oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric carbonate, ferrous carbonate, basic ferric carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, basic magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, magnesite, siderite or dolomite;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of more than or equal to 95% according to the mass ratio of 1 (0.1-0.5), and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 80-320 ℃, and the time of the second-stage pretreatment is 5-200min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is (0.1-5):1, the temperature for acid leaching vanadium extraction is 25-100 ℃, the time for acid leaching vanadium extraction is 0.1-6h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate for the first-stage pretreatment in the step (1).
Compared with the prior art, the invention at least has the following beneficial effects:
the method realizes leaching of vanadium in different types of stone coal vanadium ores through segmented pretreatment, the leaching rate of the vanadium can reach 96.7 percent at most, the acid consumption in the process is low, and the process continuity is strong.
Drawings
FIG. 1 is a process flow diagram provided by one embodiment of the present invention.
the present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
As shown in fig. 1, a process flow provided by one embodiment of the present invention may be: mixing the leachate, an additive and stone coal vanadium ore for primary pretreatment, and performing solid-liquid separation after the primary pretreatment to obtain primary pretreatment liquid and primary pretreated stone coal, wherein the primary pretreatment liquid is used for purifying and enriching vanadium; then mixing sulfuric acid with the first-stage pretreated stone coal, and performing second-stage pretreatment at a higher temperature to obtain second-stage pretreated stone coal; wherein, the acid mist formed in the second-stage pretreatment process is absorbed by water, and the absorption liquid is used for the subsequent acid leaching and vanadium extraction; finally, carrying out acid leaching and vanadium extraction on the obtained second-stage pretreated stone coal, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching slag; wherein the pickle liquor is returned to a first stage for pretreatment to be used as a leachate.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
Example 1：
The embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is low-vanadium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 0.74％、Fe2O3 1.23％、CaO 0.15％、MgO 0.34％、Al2O3 10.72％、K2o3.65%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 1:1, adding ferric oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric carbonate, ferrous carbonate and basic ferric carbonate to perform primary pretreatment, wherein the temperature of the primary pretreatment is 30 ℃, the time of the primary pretreatment is 10min, and then performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 3, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 95% according to the mass ratio of 1:0.3, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 320 ℃, and the time of the second-stage pretreatment is 20min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 1:1, the temperature for acid leaching vanadium extraction is 25 ℃, the time for acid leaching vanadium extraction is 0.25h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 96.7%.
example 2：
the embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is low-vanadium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 0.74％、Fe2O3 1.23％、CaO 0.15％、MgO 0.34％、Al2O3 10.72％、K2o3.65%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 2:1, adding calcium oxide, calcium hydroxide and calcium carbonate to perform first-stage pretreatment at a temperature of 25 ℃ for 120min, and performing solid-liquid separation to obtain first-stage pretreated stone coal and first-stage pretreatment liquid with a pH value of 1.5, wherein the first-stage pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 97% according to the mass ratio of 1:0.35, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 100 ℃, and the time of the second-stage pretreatment is 5min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 2:1, the temperature for acid leaching vanadium extraction is 45 ℃, the time for acid leaching vanadium extraction is 6 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 90.0%.
Example 3：
the embodiment providesA method for extracting vanadium by two-stage pretreatment acid leaching of stone coal vanadium ore comprises the following main components in percentage by weight: v2O5 0.74％、Fe2O3 1.23％、CaO 0.15％、MgO 0.34％、Al2O3 10.72％、K2O3.65%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 5:1, adding magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate and basic magnesium carbonate to perform primary pretreatment, wherein the temperature of the primary pretreatment is 80 ℃, the time of the primary pretreatment is 30min, and then performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 1, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 98% according to the mass ratio of 1:0.15, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 180 ℃, and the time of the second-stage pretreatment is 40min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 5:1, the temperature for acid leaching vanadium extraction is 50 ℃, the time for acid leaching vanadium extraction is 1h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate of the first-stage pretreatment in the step (1).
through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 87.8%.
Comparative example 1：
the difference from example 3 is that no additives are added in step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 78.2%.
Comparative example 2：
The method is different from the example 3 in that the acid leaching of the step (3) is directly carried out after the step (1) is finished, wherein the concentration of the sulfuric acid used in the step (3) is the same as that of the acid liquor used in the step (3) in the example 3. The leaching rate of vanadium in the stone coal vanadium ore is 2.7 percent through detection and calculation.
comparative example 3：
The difference from the example 3 is that the second-stage pretreatment of the step (2) and the acid leaching of the step (3) are directly carried out without the step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 72.7%.
Example 4：
the embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron high-calcium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 1.16％、Fe2O3 7.56％、CaO 3.27％、MgO 1.12％、Al2O3 8.96％、K2O4.71%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 0.1:1, adding magnesite, siderite and dolomite for primary pretreatment at a temperature of 100 ℃ for 60min, and then performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 2, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 95% according to the mass ratio of 1:0.2, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 80 ℃, and the time of the second-stage pretreatment is 120min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 0.1:1, the temperature for acid leaching vanadium extraction is 55 ℃, the time for acid leaching vanadium extraction is 3 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 86.7%.
Example 5：
the true bookthe embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron high-calcium mica type stone coal, and comprises the following main components in percentage by weight: v2O5 1.16％、Fe2O3 7.56％、CaO 3.27％、MgO 1.12％、Al2O3 8.96％、K2O4.71%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 0.5:1, adding iron oxide, magnesium oxide and calcium oxide to perform primary pretreatment at the temperature of 70 ℃ for 90min, and performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with the pH value of 2.5, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with 96.5% sulfuric acid according to the mass ratio of 1:0.25, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 220 ℃, and the time of the second-stage pretreatment is 220min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 0.5:1, the temperature for acid leaching vanadium extraction is 70 ℃, the time for acid leaching vanadium extraction is 4 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 95.4%.
Example 6：
the embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron high-calcium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 1.16％、Fe2O3 7.56％、CaO 3.27％、MgO 1.12％、Al2O3 8.96％、K2O4.71%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 3:1, adding ferric hydroxide, magnesium hydroxide and calcium hydroxide to perform first-stage pretreatment at a temperature of 50 ℃ for 45min, and performing solid-liquid separation to obtain first-stage pretreated stone coal and first-stage pretreatment liquid with a pH value of 2.2, wherein the first-stage pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 95% according to the mass ratio of 1:0.2, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 250 ℃, and the time of the second-stage pretreatment is 60min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 3:1, the temperature for acid leaching vanadium extraction is 65 ℃, the time for acid leaching vanadium extraction is 2 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 92.7 percent.
Comparative example 4：
the difference from example 6 is that no additives are added in step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 83.3 percent.
comparative example 5：
The difference from the example 6 is that the acid leaching of the step (3) is directly carried out after the step (1) is finished, wherein the concentration of the sulfuric acid used in the step (3) is the same as that of the acid solution used in the step (3) in the example 6. Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 3.6%.
Comparative example 6：
The difference from the example 6 is that the second-stage pretreatment of the step (2) and the acid leaching of the step (3) are directly carried out without the step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 32.7%.
example 7：
The embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 0.87％、Fe2O3 3.84％、CaO 1.68％、MgO 0.73％、Al2O3 11.68％、K2O4.54%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 4:1, adding ferric hydroxide to perform primary pretreatment at a temperature of 60 ℃ for 150min, and performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 3.5, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 97% according to the mass ratio of 1:0.25, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 270 ℃, and the time of the second-stage pretreatment is 90min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 4:1, the temperature for acid leaching vanadium extraction is 60 ℃, the time for acid leaching vanadium extraction is 5 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate of the first-stage pretreatment in the step (1).
through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 93.3%.
Example 8：
The embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 0.87％、Fe2O3 3.84％、CaO 1.68％、MgO 0.73％、Al2O3 11.68％、K2O4.54%, the method comprising the steps of:
(1) mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 2.5:1, adding calcium oxide and magnesium oxide for primary pretreatment at 65 ℃ for 300min, and then performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 4, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 97.5% according to the mass ratio of 1:0.1, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 290 ℃, and the time of the second-stage pretreatment is 15min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 2.5:1, the temperature for acid leaching vanadium extraction is 80 ℃, the time for acid leaching vanadium extraction is 4 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 88.7 percent.
example 9：
The embodiment provides a method for extracting vanadium from stone coal vanadium ore by two-stage pretreatment and acid leaching, wherein the stone coal vanadium ore is high-iron mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 0.87％、Fe2O3 3.84％、CaO 1.68％、MgO 0.73％、Al2O3 11.68％、K2O4.54%, the method comprising the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 1.5:1, adding magnesium hydroxide for primary pretreatment at 40 ℃, carrying out primary pretreatment for 75min, and carrying out solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 2.8, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 95% according to the mass ratio of 1:0.4, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 150 ℃, and the time of the second-stage pretreatment is 45min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 1.5:1, the temperature for acid leaching vanadium extraction is 40 ℃, the time for acid leaching vanadium extraction is 0.1h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 91.3%.
Comparative example 7：
the difference from example 9 is that no additives are added in step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 80.2 percent.
Comparative example 8：
the difference from the example 9 is that the acid leaching of the step (3) is directly carried out after the step (1) is finished, wherein the concentration of the sulfuric acid used in the step (3) is the same as that of the acid solution used in the step (3) in the example 9. Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 5.9%.
Comparative example 9：
The difference from the example 9 is that the second-stage pretreatment of the step (2) and the acid leaching of the step (3) are directly carried out without the step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 45.4%.
Example 10：
The embodiment provides a two-stage pretreatment acid leaching vanadium extraction method for stone coal vanadium ore, wherein the stone coal vanadium ore is high-calcium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 1.26％、Fe2O3 0.59％、CaO 6.35％、MgO 2.17％、Al2O3 7.62％、K2O2.16%, the method comprising the steps of:
(1) Mixing the leachate with stone coal vanadium ore of-40 meshes according to the liquid-solid ratio of 3.5:1, and adding calcium carbonate. Magnesium carbonate, calcium hydroxide and magnesium hydroxide are subjected to primary pretreatment, the temperature of the primary pretreatment is 55 ℃, the time of the primary pretreatment is 105min, then solid-liquid separation is carried out, primary pretreated stone coal and primary pretreated liquid with the pH value of 2.6 are obtained, and the primary pretreated liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 97% according to the mass ratio of 1:0.5, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 200 ℃, and the time of the second-stage pretreatment is 30min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 2.5:1, the temperature for acid leaching vanadium extraction is 30 ℃, the time for acid leaching vanadium extraction is 2 hours, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 95.9%.
Example 11：
the embodiment provides a two-stage pretreatment acid leaching vanadium extraction method for stone coal vanadium ore, wherein the stone coal vanadium ore is high-calcium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 1.26％、Fe2O3 0.59％、CaO 6.35％、MgO 2.17％、Al2O3 7.62％、K2o2.16%, the method comprising the steps of:
(1) mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 0.75:1, adding siderite to perform first-stage pretreatment at a temperature of 75 ℃ for 135min, and performing solid-liquid separation to obtain first-stage pretreated stone coal and first-stage pretreatment liquid with a pH value of 3.5, wherein the first-stage pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of 95% according to the mass ratio of 1:0.3, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 125 ℃, and the time of the second-stage pretreatment is 75min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) And (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 0.75:1, the temperature for acid leaching vanadium extraction is 90 ℃, the time for acid leaching vanadium extraction is 0.5h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 92.5 percent.
example 12：
the embodiment provides a two-stage pretreatment acid leaching vanadium extraction method for stone coal vanadium ore, wherein the stone coal vanadium ore is high-calcium mica type stone coal, and the main components and the contents of the stone coal vanadium ore are respectively as follows: v2O5 1.26％、Fe2O3 0.59％、CaO 6.35％、MgO 2.17％、Al2O3 7.62％、K2O2.16%, the method comprising the steps of:
(1) mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio of 0.25:1, adding dolomite for primary pretreatment at a temperature of 90 ℃ for 165min, and then performing solid-liquid separation to obtain primary pretreated stone coal and primary pretreatment liquid with a pH value of 4, wherein the primary pretreatment liquid is used for purifying and enriching vanadium;
(2) Mixing the first-stage pretreated stone coal obtained in the step (1) with 96% sulfuric acid according to the mass ratio of 1:0.225, and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 300 ℃, and the time of the second-stage pretreatment is 150min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is 0.25:1, the temperature for acid leaching vanadium extraction is 100 ℃, the time for acid leaching vanadium extraction is 1.5h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leaching liquid of the first-stage pretreatment in the step (1).
Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 94.3%.
comparative example 10：
The difference from example 12 is that no additives are added in step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 82.9%.
comparative example 11：
The difference from the example 12 is that the acid leaching of the step (3) is directly carried out after the step (1) is finished, wherein the concentration of the sulfuric acid used in the step (3) is the same as that of the acid solution used in the step (3) in the example 12. Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 4.2%.
Comparative example 12：
The difference from the example 12 is that the second-stage pretreatment of the step (2) and the acid leaching of the step (3) are directly carried out without the step (1). Through detection and calculation, the leaching rate of vanadium in the stone coal vanadium ore is 39.6%.
In the examples, the solid-liquid separation modes of the steps (1) and (3) are filtration.
It can be seen from the above examples and comparative examples that the method realizes the high-efficiency leaching of vanadium in different types of stone coal vanadium ores by two-stage pretreatment of the stone coal vanadium ores, especially by adding additives in the pretreatment stage, the leaching rate of vanadium can reach 96.7% at most, and the process has low acid consumption and strong process continuity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
in addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The method for extracting vanadium by two-stage pretreatment acid leaching of stone coal vanadium ore is characterized by comprising the following steps of:
(1) Adding stone coal vanadium ore and an additive into the leaching solution to carry out primary pretreatment, and carrying out solid-liquid separation to obtain primary pretreatment solution and primary pretreated stone coal;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid, and performing second-stage pretreatment to obtain second-stage pretreated stone coal;
(3) and (3) performing acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, performing solid-liquid separation to obtain acid leaching solution and acid leaching slag, wherein the acid leaching solution is used as the leaching solution of the first-stage pretreatment in the step (1).
2. The method of claim 1, wherein the stone coal vanadium ore of step (1) is crushed and ball milled to a particle size of-40 mesh.
3. The method of claim 1 or 2, wherein the additive in step (1) is one or a combination of at least two of iron oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric carbonate, ferrous carbonate, basic ferric carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, basic magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, magnesite, siderite or dolomite;
preferably, the pH value of the first-stage pretreatment liquid is 1-4, preferably 1.5-3.
4. A process according to any one of claims 1 to 3, wherein the liquor-to-solid ratio of leach liquor from the first stage of pretreatment in step (1) to stone coal vanadium ore is (0.1 to 5) to 1, preferably (0.25 to 2.5) to 1;
Preferably, the temperature of the primary pretreatment in the step (1) is 25-100 ℃, preferably 30-80 ℃;
Preferably, the time of the pretreatment in the step (1) is 10-300min, preferably 30-180 min;
preferably, the primary pretreatment solution of the step (1) is used for purifying and enriching vanadium.
5. The method according to any one of claims 1 to 4, wherein the sulfuric acid concentration in step (2) is 95% or more;
Preferably, the mass ratio of the stone coal to the sulfuric acid in the primary pretreatment is 1 (0.1-0.5), preferably 1 (0.15-0.3).
6. The method according to any one of claims 1 to 5, wherein the temperature of the secondary pretreatment in step (2) is 80 to 320 ℃, preferably 100 to 300 ℃;
Preferably, the time of the two-stage pretreatment in the step (2) is 5-200min, preferably 20-120 min.
7. The method according to any one of claims 1 to 6, wherein acid mist is generated during the secondary pretreatment in step (2), and preferably the acid mist is absorbed by water.
8. The method of claim 7, wherein the acid solution used in the acid leaching vanadium in the step (3) is a water absorption solution of the acid mist in the secondary pretreatment in the step (2);
Preferably, the liquid-solid ratio of the acid solution to the second-stage pretreated stone coal in the step (3) is (0.1-5):1, preferably (0.25-2.5): 1.
9. the process according to any one of claims 1 to 8, wherein the temperature of the acid leaching of vanadium in step (3) is between 25 and 100 ℃, preferably between 30 and 80 ℃;
Preferably, the time for acid leaching vanadium in the step (3) is 0.1-6h, preferably 0.25-3 h.
10. The method according to claims 1-9, characterized in that the method comprises the steps of:
(1) Mixing the leachate with-40-mesh stone coal vanadium ore according to a liquid-solid ratio (0.1-5):1, adding an additive to perform first-stage pretreatment at a temperature of 25-100 ℃ for 10-300min, and performing solid-liquid separation to obtain first-stage pretreated stone coal and first-stage pretreatment liquid with a pH value of 1-4, wherein the first-stage pretreatment liquid is used for purifying and enriching vanadium; wherein the additive is any one or the combination of at least two of ferric oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric carbonate, ferrous carbonate, basic ferric carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, basic magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, magnesite, siderite or dolomite;
(2) mixing the first-stage pretreated stone coal obtained in the step (1) with sulfuric acid with the concentration of more than or equal to 95% according to the mass ratio of 1 (0.1-0.5), and then performing second-stage pretreatment, wherein the temperature of the second-stage pretreatment is 80-320 ℃, and the time of the second-stage pretreatment is 5-200min, so as to obtain second-stage pretreated stone coal; wherein, acid mist generated in the second-stage pretreatment process is absorbed by water;
(3) and (3) carrying out acid leaching on the second-stage pretreated stone coal obtained in the step (2) to extract vanadium, wherein acid liquor used for acid leaching vanadium extraction is water absorption liquid of acid mist in the second-stage pretreatment in the step (2), the liquid-solid ratio of the acid liquor to the second-stage pretreated stone coal is (0.1-5):1, the temperature for acid leaching vanadium extraction is 25-100 ℃, the time for acid leaching vanadium extraction is 0.1-6h, solid-liquid separation is carried out to obtain acid leaching liquid and acid leaching slag, and the acid leaching liquid is used as leachate for the first-stage pretreatment in the step (1).
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