• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for extracting vanadium from shale, comprising: a) grinding the shale into fine powders, mixing the fine powders with an additive in a mass ratio of 1: 0.04 to 0.12 to give a mixture, heating the mixture to a temperature between 850 and 950 ° C at a heating rate of 5 to 9 ° C / min, and cooking the mixture for between 30 and 90 min; b) immersing a product in water and acid respectively to give a first solution and a second solution, the combination of the two solutions, and carrying out adsorption by ion exchange on the combined solution using a macroporous anion exchange resin based on styrene-divinylbenzene; and c) performing the desorption, purification and precipitation to give poly (ammonium vanadate), and calcination of poly (ammonium vanadate) at a temperature between 450 and 530 ° C for between 20 and 50 min to give V205.
    公开号:BE1021589B1
    申请号:E2013/0644
    申请日:2013-09-26
    公开日:2015-12-16
    发明作者:Yimin Zhang；Xiaobo Zhu；Tao Liu；Jing Huang；Tiejun Chen；Shenxu Bao
    申请人:Wuhan University Of Technology；
    IPC主号:
    专利说明:

    Process for extracting vanadium from shale containing vanadium
    Field of the Invention The invention relates to the field of vanadium extraction, and more particularly to a process for extracting vanadium from shale. Background of the invention
    The vanadium-containing shale has become a very important vanadium resource because of its abundant reserves, and the extraction of vanadium element in the form of V205 from vanadium-containing shale is an important route. Vanadium in the vanadium-containing schist exists primarily in the form of crystalline structures of mica in an isomorphic state, so that it can not be directly soluble in water, an alkaline solution, or any diluted acid other than hydrofluoric acid. Given such characteristics, high temperature cooking and strong acid leaching are generally used to destroy the crystalline structure of mica in the vanadium-containing shale to allow vanadium in shale to be water-soluble. , the acid, or an alkaline solution and be transformed into a vanadate for further processing. Typical processes for extracting vanadium from shale include: 1. Sodium chloride cooking - water leaching - ion exchange - vanadium precipitation by ammonium salt.
    The process uses an additive comprising NaCl and Na2CO3, and a dosage of the additive exceeds 12% by weight. A large amount of NaCl leads to severe pollution by Cl2 and HCl. The document "Additive composition for extracting vanadate" (Publication No. CN1884597 A) disclosed an additive composition comprising sodium chloride, sodium carbonate, and transition metals. A sodium chloride content in the additive composition is 50%, and a dosage of the additive composition is 15% of the total raw materials, thus, the cooking process produces severe pollution. In addition, the leaching rate and the vanadium recovery rate are very low. 2. Blank firing - alkali leaching - extraction - vanadium precipitation by ammonium salt.
    The process uses a 2 mol / l NaOH solution as leaching agent and requires a high consumption of alkali. A resulting leached solution contains a large amount of silicon impurities, which seriously influences the subsequent extraction process (He, DS, Feng, QM, Zhang, GF, Ou, LM, and Lu, YP Environmentally-f riendly method for extracting vanadium from vanadium-containing shale [J] Mining and Metallurgical Engineering, 2007, 20: 1184-1186). 3. Direct acid leaching (or acid leaching under pressure) - extraction - precipitation of vanadium with ammonium salt.
    The process employs a 4 mol / l sulfuric acid solution as a leaching agent and requires high acid consumption. In addition, a large amount of alkali is required to adjust the pH value to meet the requirements of the subsequent extraction process (Yang, JD, and Jin, X.). Journal of Beijing University of Chemical Technology, 2007, 34 (3): 254-257). The pressure-extraction acid leaching process for extracting vanadium consumes a large amount of energy, and uses 25 to 40% by weight of sulfuric solution as leaching agent. The process requires a high consumption of acid, and a resulting leached acid solution comprises a high content of impurities, which seriously affects the subsequent operations (Li, ΜT, Wei, C., Fan, G., Li, CX, Deng, ZG, and Li, XB Study on vanadium extraction from vanadium-containing shale by pressurized acid leaching [J.] Journal of Nonferrous Metals, 2010, 20: 112-117). Summary of the invention
    In view of the problems described above, an object of the invention is to provide a vanadium extraction process from shale whose process is simple and industrialization is practical, and which is capable of significantly improving the leaching rate and recovery rate of vanadium.
    To achieve the above objective, the invention provides a process for extracting vanadium from shale, the process comprising the following steps: a) grinding the shale into fine powders, mixing the fine powders with an additive in a weight ratio of 1: 0.04 to 0.12 to give a mixture, heating the mixture to a temperature of between 850 and 950 ° C at a heating rate of 5 to 9 ° C / min, and cooking of mixing for 30 to 90 minutes; b) immersion of a product resulting from cooking in water to give a first solution and a sediment, immersion of the sediment with an acid to give a second solution and a rejection, the combination of the first and second solutions to give a combined solution, and carrying out ion exchange adsorption on the combined solution using a styrene-divinylbenzene macroporous anion exchange resin; and c) desorbing the styrene-divinylbenzene macroporous anion exchange resin to provide a desorption solution, purifying the desorption solution to provide a purified solution, precipitating the purified solution to yield poly ( ammonium vanadate), and calcining the poly (ammonium vanadate) at a temperature between 450 and 530 ° C for between 20 and 50 min to give vanadium oxide (V205).
    Between 60 and 90% by weight of the fine powders have a particle size of not more than 0.178 mm.
    The shale is a shale containing mica vanadium comprising more than 5% by weight of calcium oxide. The additive is a mixture of K2SO4, Na2SO4 and NaCl, and a weight ratio thereof is from 1: 0.2 to 0.5: 0.1 to 0.2. The immersion in water is carried out under the following conditions: an immersion temperature between 50 and 90 ° C, a solid-liquid mass ratio of 1: 1.5 to 2.5, a stirring speed between 100 and 250 rpm, and stirring time between 20 and 40 min. The immersion in the acid is carried out under the following conditions: an immersion temperature between 80 and 95 ° C, H2SO4 at 1 to 3% v / v being used in a solid-liquid mass ratio of 1: 1 to 2, a stirring speed between 100 and 250 rpm and a stirring time between 30 and 60 min.
    A desorption agent comprising 3 to 5% by weight of NaOH and 8 to 12% by weight of NaCl is used for the desorption, and a volume dosage thereof is 1 to 3 times that of the exchange resin. macroporous anions based on styrene-divinylbenzene.
    The desorption solution is purified using an alkali-soluble calcium salt as a cleaning agent, and a dosage of the cleaning agent is between 6 and 18 grams per liter of the desorption solution.
    The purified solution is precipitated as follows: at a temperature between 93 and 99 ° C, 40% v / v H2SO4 is first added to the purified solution to adjust its pH value to 2, 2 to 2.5, then a precipitant comprising an acid-soluble ammonium salt is added to the purified solution for precipitation, an assay of the precipitant being in accordance with the following ratio: a molar ratio between the ammonium ions in the ammonium salt and vanadium ions in the purified solution being 3 to 6: 1. The additive comprises a small amount of NaCl, which facilitates the destruction of the vanadium-containing mica structure, shortens the cooking time, and improves the cooking effect. The functions of Na2SO4 and K2SO4 are as follows: on the one hand, S02 decomposed from a sulphate in the cooking process reacts with CaO in the shale to produce CaSO4, thus inhibiting the production of anorthite and calcium vanadate; on the other hand, Na 2 O and K 2 O decomposed from sulfate react readily with V 2 O 5, Al 2 O 3, and SiO 2 to produce K and Na feldspar, sodium vanadate, and potassium vanadate. Since the melting temperature range of K and Na feldspar is relatively high, sodium vanadate and potassium vanadate are soluble in water and are not prone to being wrapped, improving the solubility of vanadium in water. . H 2 SO 4 at 1 to 3% v / v is used to extract a water-insoluble vanadate from the sediment resulting from water leaching; 75 to 79% of the water-insoluble vanadate is extracted with H2SO4, which is easy to control, thus facilitating its industrialization. The combined solution of the first and second solutions has a pH value exceeding 2, so that the ion exchange can be carried out directly without addition of alkali to further adjust the pH value, thus simplifying the process. An adsorption rate of vanadate is 98 to 99% by weight, a vanadate desorption rate is 98 to 99% by weight, a vanadate precipitation rate is 99 to 99.8% by weight, a purity V205 is 99.12 to 99.63% by weight, and a recovery rate of vanadate is 72 to 75%.
    Thus, the process of the invention is advantageous because of its simplified process, practical industrialization, leaching rate and greatly improved vanadate recovery rate.
    Brief description of the drawings
    Figure 1 is a process flow diagram of a vanadium extraction process from shale.
    Detailed Description of the Embodiments
    To further illustrate the invention, experiments detailing a process for extracting vanadium from shale are described below. It should be noted that the following examples are intended to describe and not to limit the invention.
    The raw materials and process parameters were as follows: between 60 and 90% by weight of fine powders had a particle size of not more than 0.178 mm.
    The shale was a shale containing mica vanadium comprising more than 5% by weight of calcium oxide.
    An additive was a mixture of K 2 SO 4 / Na 2 SO 4 and NaCl, and a mass ratio thereof was 1: 0.2 to 0.5: 0.1 to 0.2.
    The leaching with water was carried out under the following conditions: an immersion temperature between 50 and 90 ° C, a solid-liquid mass ratio of 1: 1.5 to 2.5, a stirring speed of 100 and 250 rpm, and stirring time between 20 and 40 min.
    The acid leaching was carried out under the following conditions: an immersion temperature between 80 and 95 ° C, H2SO4 at 1 to 3% v / v being used and a solid-liquid mass ratio of 1: 1 to 2, a stirring speed between 100 and 250 rpm, and a stirring time between 30 and 60 min.
    A desorption agent comprising 3 to 5% by weight of NaOH and 8 to 12% by weight of NaCl was used for the desorption, and a volume dosage thereof was 1 to 3 times that of the exchange resin. macroporous anion based on styrene-divinylbenzene.
    The desorption solution was purified using an alkali-soluble calcium salt such as a cleaning agent, and a dosage of the cleaning agent was between 6 and 18 grams per liter of the desorption solution.
    The purified solution was precipitated as follows: at a temperature between 93 and 99 ° C, 40% v / v H2SO4 was first added to the purified solution to adjust its pH value to 2.2 to 2. , 5, then a precipitant comprising an acid soluble ammonium salt was added to the purified precipitation solution, an assay of the purifier being in accordance with the following ratio: a molar ratio of ammonium ions in the sodium salt; ammonium and vanadium ions in the purified solution being from 3 to 6: 1.
    Example 1
    Process for extracting vanadium from shale. The shale was ground into fine powders. The fine powders were mixed with the additive in a weight ratio of 1: 0.04 to 0.06 to give a mixture. Then, the mixture was heated at a temperature between 92 ° and 950 ° C at a heating rate between 5 and 9 ° C / min, and baked for between 30 and 50 min.
    A product of cooking was immersed in water to produce a first solution and a sediment. The sediment was then immersed in acid to produce a second solution and a rejection. After that, the first and second solutions were combined to give a combined solution. The ion exchange adsorption was performed on the combined solution using a macroporous anion exchange resin based on styrene-divinylbenzene.
    The styrene-divinylbenzene macroporous anion exchange resin was desorbed to give a desorption solution. Then, the desorption solution was purified to give a purified solution. The acid soluble ammonium salt was added to the purified solution to allow an ammonium poly (vanadate) to precipitate. The poly (ammonium vanadate) was then calcined at 450-500 ° C for 20-40 min to give vanadium oxide (V205).
    A vanadium leach rate was between 75 and 77% by weight, a vanadium adsorption rate was between 98 and 99% by weight, a vanadium desorption rate was between 98 and 99% by weight, a precipitation rate of vanadium was between 99 and 99.6% by weight, and a purity of V205 was between 99.12 and 99.43% by weight.
    Example 2
    Process for extracting vanadium from shale. The shale was ground into fine powders. The fine powders were mixed with the additive in a weight ratio of 1: 0.06 to 0.09 to give a mixture. Then, the mixture was heated to a temperature between 880 and 920 ° C at a heating rate between 5 and 9 ° C / min, and baked for between 50 and 70 min.
    A product of cooking in water was immersed to produce a first solution and a sediment. The sediment was then immersed in the acid to produce a second solution and a rejection. After that, the first and second solutions were combined to give a combined solution. The ion exchange adsorption was performed on the combined solution using a macroporous anion exchange resin based on styrene-divinylbenzene.
    The styrene-divinylbenzene macroporous anion exchange resin was desorbed to give a desorption solution. Then, the desorption solution was purified to give a purified solution. The acid soluble ammonium salt was added to the purified solution to allow an ammonium poly (vanadate) to precipitate. The poly (ammonium vanadate) was then calcined at a temperature between 460 and 510 ° C for between 30 and 50 min to give V205.
    A vanadium leach rate was between 76 and 78% by weight, a vanadium adsorption rate was between 98 and 99% by weight, a vanadium desorption rate was between 98 and 99% by weight, a precipitation rate of vanadium was between 99.2 and 99.7% by weight, and a purity of V205 was between 99.24 and 99.54% by weight.
    Example 3
    Process for extracting vanadium from shale. The shale was ground into fine powders. The fine powders were mixed with the additive in a weight ratio of 1: 0.09 to 0.12 to give a mixture. Then, the mixture was heated to a temperature between 850 and 880 ° C at a heating rate between 5 and 9 ° C / min, and baked for between 70 and 90 min.
    A cooking product was immersed in water to produce a first solution and a sediment. The sediment was then immersed in the acid to produce a second solution and a rejection. After that, the first and second solutions were combined to give a combined solution. The ion exchange adsorption was carried out on the combined solution using a macroporous anion exchange resin based on styrene-divinylbenzene.
    The styrene-divinylbenzene macroporous anion exchange resin was desorbed to give a desorption solution. Then, the desorption solution was purified to give a purified solution. The acid soluble ammonium salt was added to the purified solution to allow an ammonium poly (vanadate) to precipitate. The poly (ammonium vanadate) was then calcined at a temperature between 470 and 530 ° C for 25 to 45 minutes to give V2O5.
    A vanadium leach rate was between 77 and 79% by weight, a vanadium adsorption rate was between 98 and 99% by weight, a vanadium desorption rate was between 98 and 99% by weight, a precipitation rate of vanadium was between 99.4 and 99.8% by weight, and a purity of V205 was between 99.43 and 99.63% by weight. The additive comprises a small amount of NaCl, which facilitates the destruction of the vanadium-containing mica structure, shortens the cooking time, and improves the cooking effect. The functions of Na2SO4 and K2SO4 are as follows: first, SO2 decomposed from a sulphate in the cooking process reacts with CaO in the shale to produce CaSO4, thus inhibiting the production of anorthite and calcium vanadate; on the other hand, Na 2 O and K 2 O decomposed from sulfate react readily with V 2 O 5, Al 2 O 3 (and SiO 2 to produce K and Na feldspar, sodium vanadate, and potassium vanadate. Since melting temperatures of K and Na feldspar are relatively high, sodium vanadate and potassium vanadate are soluble in water and are not prone to being wrapped, thus improving the solubility of vanadium in water. H2S04 at 1 to 3% v / v is used to extract a water-insoluble vanadate from the sediment resulting from water leaching, 75 to 79% of the water-insoluble vanadate is extracted with H2SO4, the The process is easy to control, facilitating its industrialization.The combined solution of the first and second solutions has a pH value exceeding 2, so that ion exchange can be carried out directly without adding alkali to further adjust the value. pH, simplifian Thus the process A vanadate adsorption rate is 98 to 99% by weight, a vanadate desorption rate is 98 to 99% by weight, a vanadate precipitation rate is 99 to 99.8% by weight, a purity of V205 is from 99.12 to 99.63% by weight, and a recovery rate of vanadate is 72 to 75%.
    Thus, the process of the invention is advantageous because of its simplified process, its practical industrialization, its leaching rate and its greatly improved vanadate recovery rate.
    权利要求:
    Claims (9)
    [1]
    1. A process for extracting vanadium from shale, the process comprising the following steps: a) grinding the shale into fine powders, mixing the fine powders with an additive in a weight ratio of 1: 0.04 to 0.12 to give a mixture, heating the mixture to a temperature between 850 and 950 ° C at a heating rate of 5 to 9 ° C / min, and baking the mixture for between 30 and 90 min; b) immersion of a product resulting from cooking in water to give a first solution and a sediment, immersion of the sediment with an acid to give a second solution and a rejection, the combination of the first and second solutions to give a combined solution, and carrying out ion exchange adsorption on the combined solution using a macroporous anion exchange resin based on styrene-divinylbenzene; and c) desorbing the styrene-divinylbenzene macroporous anion exchange resin to provide a desorption solution, purifying the desorption solution to provide a purified solution, precipitating the purified solution to yield poly ( ammonium vanadate), and calcining the ammonium poly (vanadate) at a temperature between 450 and 530 ° C for between 20 and 50 min to give vanadium oxide (V205).
    [2]
    2. A process according to claim 1, characterized in that between 60 and 90% by weight of the fine powders have a particle size of not more than 0.178 mm.
    [3]
    3. - Process according to claim 1, characterized in that the shale is a shale containing mica vanadium comprising more than 5% by weight of calcium oxide.
    [4]
    4. - Process according to claim 1, characterized in that the additive is a mixture of K2SO4 / Na2SO4, and NaCl, and its weight ratio is from 1: 0.2 to 0.5: 0.1 to 0.2 .
    [5]
    5. - Method according to claim 1, characterized in that the immersion in water is carried out under the following conditions: an immersion temperature between 50 and 90 ° C, a solid-liquid mass ratio of 1: 1, 5 to 2.5, a stirring speed between 100 and 250 rpm, and a stirring time between 20 and 40 min.
    [6]
    6. - Process according to claim 1, characterized in that the immersion in the acid is carried out under the following conditions: an immersion temperature between 80 and 95 ° C, H2SO4 at 1 to 3% v / v being employed as well as a solid-liquid mass ratio of 1: 1 to 2, a stirring speed between 100 and 250 rpm, and a stirring time between 30 and 60 min.
    [7]
    7. - Process according to claim 1, characterized in that a desorption agent comprising 3 to 5% by weight of NaOH and 8 to 12% by weight of NaCl is used for the desorption, and a dosing volume thereof. it is 1 to 3 times that of the macroporous anion exchange resin based on styrene-divinylbenzene.
    [8]
    8. - Process according to claim 1, characterized in that the desorption solution is purified using an alkali-soluble calcium salt as a cleaning agent, and a dosage of the cleaning agent is between 6 and 18 g per liter of the desorption solution.
    [9]
    9. - Process according to claim 1, characterized in that the purified solution is precipitated as follows: at a temperature between 93 and 99 ° C, is first added with 40% v / v H2SO4 to the purified solution for adjust its pH value to 2.2 to 2.5, then a precipitant comprising an acid soluble ammonium salt is added to the purified precipitation solution, a dosage of the precipitant being in accordance with the following ratio: molar ratio between the ammonium ions in the ammonium salt and the vanadium ions in the purified solution being 3 to 6: 1.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CN201210455|2012-11-14|
    CN201210455607.XA|CN102925720B|2012-11-14|2012-11-14|Method for extracting vanadium from shale containing vanadium|
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