Patent Application
20130195737
1. Field of the Invention
The invention relates to a hydrometallurgical field, and more particularly to a method for extracting tungsten from scheelite.
2. Description of the Related Art
A typical method for processing scheelite is autoclaving using suda as a leaching agent. The method can stably decompose scheelite, and a final WO3 in a residue can be controlled 1% below; however, the practical dosage of the reagent is too large which is about three times of the theoretical dosage. Sometimes in the lab experiment, the practical dosage is even 5-6 times of the theoretical dosage. Furthermore, the operation temperature is very high, about 225° C., and the pressure of the device is 20 atm.
Another method for processing scheelite is autoclaving using NaOH as a leaching agent, and more than 80% of APT production of China is produced by this method. The method is carried out with a large amount of NaOH having a high concentration being added, at a high temperature and pressure, so that the scheelite can be effectively decomposed, and WO3 in the residues can be lowered to 1-3%. However, the technique has a large energy consumption, high production cost, and large amount of waste water in the subsequent process.
Acid decomposition is a method that mainly uses hydrochloric acid to process scheelite concentrate. A thermodynamic study on such a method has proved that it has a very high reaction trend. However, during the hydrochloric acid decomposition, tungstic acid is in a form of yellow gel wrapping an inner undecomposed scheelite, which results in incomplete decomposition. Besides, the hydrochloric acid has serious problems of acid corrosion and volatilization, which causes a poor working condition. Finally, after treating the remnant mother liquor of hydrochloric acid with a lime, a large amount of CaCl2 solution produced is discharged. This method has been discarded.
Because tungsten together with phosphorus, arsenic, silicon, and other impurities can form a soluble heteropoly acid (for example, [PW12O40]3−) having 1:6-1:12 of a ratio of impurities to tungsten; during the hydrochloric acid decomposition, even a small amount of phosphorus can cause loss of a large amount of tungsten into leaching solution, so that the hydrochloric acid decomposition is mainly used to process a scheelite concentrate having a high purity (which is required to have a very low content of phosphorus, arsenic and other impurities). However, it implies us that adding a small amount of phosphoric acid intentionally during the leaching process to cause tungsten into the solution in the form of soluble phosphotungstic heteropoly acid, the problem of tungstic acid wrapping during the hydrochloric acid decomposition can be overcome. But study has shown that the yellow tungstic acid still occurs when the dosage of phosphorus is too small, so that a large excess coefficient is needed, and the more phosphorus is used, the higher the leaching speed is. However, corrosion and volatilization problems of the hydrochloric acid still exist, and thus, the study has not been applied in industry.
To solve corrosion and volatilization problems of hydrochloric acid, and to realize the leaching of the tungsten in the form of soluble phosphotungstic heteropoly acid, sulfuric acid is considered to substitute hydrochloric acid. However, when a large amount of sulfuric acid exists, the supersaturated gypsum is quickly nucleated to form a large amount of finely crystals, which results in wrapping, and the decomposition effect is not good. During the sulfuric acid decomposition, phosphoric acid, calcium phosphate, or phosphorite is added to provide phosphorus as a complexing agent for tungsten, but a certain amount of NaCl is needed to improve the decomposition. Then, HCl in the strong sulfuric acid solution has a high degree of activity, which is equal to a high concentration of a hydrochloride acid, thus, problems like the corrosion of C− come out again.
The principle of the action of NaCl, is that the chloride ions can largely increase the induction period of the calcium sulfate crystals, thereby preventing the calcium sulfate crystals from nucleating. To a certain degree, it is helpful to form large crystals, and prevent the products from wrapping the minerals and obstructing the decomposition. However, in actual fact, adding NaCl cannot achieve an ideal decomposition result, but bring up problems like device corrosion and HCl volatilization; besides, it cannot solve the problem of tungstic acid wrapping.
Our study shows that, using a phosphoric acid solution having a high concentration (a concentration of P2O5 is 15-35%) to decompose a scheelite can largely improve the formation rate of a soluble of phosphotungstic acid, avoiding wrapping of the tungstic acid precipitation, as shown in equation (1).
12CaWO4+25H3PO4=12Ca(H2PO4)2.H2O+H3[PW12O40]+11H2O (1)
Furthermore, phosphoric acid has a low corrosive effect, and no volatilization problem like hydrochloric acid.
However, phosphoric acid has a high production cost, and a large amount of phosphorus exist in a form of Ca(H2PO4)2.H2O, which leads to difficulties in carrying out further reactions. Thus, during the decompostion process, a certain amount of H2SO4 can be added to react with the consequent Ca(H2PO4)2.H2O, so that calcium is finally precipitated in a form of calcium sulfate, and phosphoric acid is formed again, thereby lowing the consumption of phosphoric acid. The equation (2) is as follows:
Ca(H2PO4)2.H2O+H2SO4→CaSO4.nH2O+H3PO4 (2)
A total equation is:
12CaWO4+H3PO4+12H2SO4+12nH2O =12CaSO4.nH2O+H3[PW12O40]+12H2O (3)
Furthermore, the phosphoric acid solution having a high concentration can effectively lower the degree of supersaturation of calcium sulfate during the decomposition of tungsten ore. This is because phosphoric acid can complex calcium ions, thereby the solubility of the calcium sulfate increases as the concentration of the phosphoric acid increases, and reach a highest when the P2O5 is about 20 wt. %. The solubility of the calcium sulfate at the temperature of 80° C. is 5-7 times as those having no phosphoric acid. Even when P2O5 reaches to 40%, the solubility of the calcium sulfate is 3-5 times as those having no phosphoric acid. The possibility of the nucleating of the calcium sulfate is lowered. Thus, large crystals are easily to form and a compact calcium sulfate is prevented, and the scheelite is leached effectively.
Therefore, a strategic is formed that adopting a phosphoric acid having a high concentration to decompose a scheelite, and adding a certain amount of sulfuric acid to form phosphoric acid again; by which not only problems like wrapping of tungstic acid can be solved, and tungsten is into the solution in the form of phosphotungstic acid, but also a compact calcium sulfate film is prevented, and the objective of scheelite decomposition is achieved with high efficiency. Furthermore, studies have shown that, the solubility of phosphotungstic acid is largely affected by concentrations of phosphoric acid and sulfuric acid, and the reaction temperature. This characteristic has shed light on the extraction of phosphotungstic acid from the leaching agent (for example, in a system having 20 wt. % P2O5 of a concentration of phosphoric acid, the relationship between the solubility of the phosphotungstic acid, the concentration of sulfuric acid, and the temperature is shown in
In view of the above-described problems, it is one objective of the invention to provide a method for extracting tungsten from scheelite that is free of pollution, and has low cost, low energy consumption, convenient operation, and high efficiency.
To achieve the above objective, in accordance with one embodiment of the invention, there is provided a method for extracting tungsten from scheelite, the method comprising:
In a class of this embodiment, the scheelite comprises 10-75 wt. % of WO3 and has a grain size ≦150 μm.
In a class of this embodiment, the phosphotungstic acid crystals are obtained using a cooling crystallization process by cooling the filtrate to 30-50° C. and filtering; or the phosphotungstic acid crystals are obtained using a concentrated crystallization process by concentrating the filtrate to have a ⅓-⅘ original volume, and filtering.
In a class of this embodiment, the phosphotungstic acid solution obtained from dissolving the phosphotungstic acid crystals comprises 350-500 g/L of WO3; and the phosphotungstic acid solution is transformed into the ammonium tungstate solution comprising 200-300 g/L of WO3 by ammonia, ion exchange, or solvent extraction.
Advantages of the invention are summarized as follows:
The invention is described hereinbelow with reference to the accompanying drawings, in which:
To further illustrate the invention, experiments detailing a method for extracting tungsten from scheelite are described below. It should be noted that the following examples are intended to describe and not to limit the invention.
Phosphoric acid with a high concentration is adopted which can effectively lower the degree of supersaturation of calcium sulfate during the decomposition of tungsten ore. This is because phosphoric acid can complex calcium ions, so that the solubility of the calcium sulfate increases as the concentration of phosphoric acid increases, and the possibility of the nucleating of the calcium sulfate is lowered. Thus, large crystals are easy to form and a compact calcium sulfate is prevented, and the scheelite is leached effectively. Experiments are carried out as follows:
A phosphoric acid solution having 20 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution; a concentration of H2SO4 was controlled at 150 g/L. Thereafter, 5 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 70.6 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 5:1 L/kg), and the reaction was carried out for 6 h. A leaching rate of tungsten was 99.3%. An XRD map and a SEM picture of the residue are respectively shown in
When a phosphoric acid having a low concentration was adopted, experiments are carried out as follow:
A phosphoric acid solution having 5 wt. % of P2O5 was prepared. Sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution; a concentration of H2504 was controlled at 150 g/L. Thereafter, 5 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 70.6 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 5:1 L/kg), and the reaction was carried out for 6 h. A leaching rate of tungsten was 87.6%. An XRD map and a SEM picture of the residue are respectively shown in
A phosphoric acid solution having 20 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 150 g/L. Thereafter, 6 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 80° C. And then 1 kg of a sheelite having 70.6 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 6:1 L/kg), and the reaction was carried out for 6 h. A leaching rate of tungsten was 99.2%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was condensed to a volume that was equal to ⅓ of an original volume by condensed crystallization after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 85.3%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 489.3 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 250.6 g/L of WO3.
A phosphoric acid solution having 15 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 300 g/L. Thereafter, 4 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 70.6 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 4:1 L/kg), and the reaction was carried out for 4 h. A leaching rate of tungsten was 99.5%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was cooled to a temperature of 30° C. after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 82.1%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 396.7 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 262.3 g/L of WO3.
A phosphoric acid solution having 35 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 200 g/L. Thereafter, 3 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 70° C. And then 1 kg of a sheelite having 70.6 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 3:1 L/kg), and the reaction was carried out for 5 h. A leaching rate of tungsten was 99.0%. The reaction was followed with a filter process from which a filtrate was obtained. After being supplemented for a consumed sulfuric acid, the filtrate was condensed to a volume that was equal to ⅘ of an original volume by condensed crystallization. In such a condition, a crystallization rate of the phosphotungstic acid was 81.7%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 358.4 g/L of WO3. A D301 resin was used to adsorb tungsten from the phosphotungstic acid solution, an adsorption rate of tungsten was 99.1%. After desorption by an ammonia solution, an ammonium tungstate solution having 209.3 g/L of WO3 was obtained; and a solution after an ion exchange was used to dissolve phosphotungstic acid crystals.
A phosphoric acid solution having 35 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 500 g/L. Thereafter, 8 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 65.7 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 8:1 L/kg), and the reaction was carried out for 1 h. A leaching rate of tungsten was 99.0%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was cooled to a temperature of 50° C. after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 62.7%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 404.1 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 228.7 g/L of WO3.
A phosphoric acid solution having 25 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 250 g/L. Thereafter, 4 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 100° C. And then 1 kg of a sheelite having 65.7 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 4:1 L/kg), and the reaction was carried out for 3 h. A leaching rate of tungsten was 99.3%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was cooled to a temperature of 40° C. after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 67.1%. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 425.8 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 231.4 g/L of WO3.
A mother liquor was obtained after the crystallization of Example 6. After being supplemented for sulfuric acid, a phosphoric acid solution, and water to make the solution having 25 wt. % of P2O5, and 250 g/L of a concentration of H2SO4, the mother liquor was used for decomposing 1 kg of a scheelite having 65.7 wt. % of WO3. A liquid-solid ratio was controlled at 4:1 L/kg, and the reaction was carried out at a temperature of 100° C. for 3 h. A leaching rate of tungsten was 99.2%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was condensed to a volume that was equal to ½ of an original volume by condensed crystallization after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 86.4%. After another filter, a new mother liquor was obtained; after being supplemented for phosphoric acid and water to an original level, the new mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in water to obtain a phosphotungstic acid solution having 367.3 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 253.8 g/L of WO3, 2.4 g/L of P, and 25.6 g/L of SO42−. An ammonium magnesium salt method was adopted to remove impurities. A MgCl2 solution having 200 g/L of MgCl2 was added according to 1.2 of a mol ratio of Mg to P, the reaction was maintained for 30 min at a room temperature, then a filter was carried out, after which a removal rate of phosphorus was 99.9%, and a loss of tungsten was only 0.05 wt. %. Mo was removed according to a method disclosed in Pat. No. 97108113.1, and a consequent solution was crystallized by volatilization to obtain an ammonium paratungstate (APT) crystals. The crystallization rate of APT was 94.5%. Analysis results of the products are shown in Table 1.
A phosphoric acid solution having 35 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 300 g/L. Thereafter, 5 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 45.9 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 6:1 L/kg), and the reaction was carried out for 6 h. A leaching rate of tungsten was 99.0%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was condensed to a volume that was equal to ⅔ of an original volume by condensed crystallization after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 84.7%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 376.8 g/L of WO3 which was then extracted using a primary amine as an extractant, and an extraction rate of tungsten was 98.8%. Thereafter, an ammonia solution was used to stripping to obtain an ammonium tungstate solution having 205.2 g/L of WO3. A liquor from the extraction was used to dissolve the phosphotungstic acid crystals.
A phosphoric acid solution having 25 wt. % of P2O5 was prepared, and sulfuric acid was added and mixed with the phosphoric acid solution to obtain a mixed acid solution, a concentration of H2SO4 was controlled at 500 g/L. Thereafter, 3 L of the mixed acid solution was added into the decomposition reactor, and was heated to a temperature of 90° C. And then 1 kg of a sheelite having 30.4 wt. % of WO3 was added into the decomposition reactor (liquid-solid ratio was at 3:1 L/kg), and the reaction was carried out for 4 h. A leaching rate of tungsten was 98.9%. The reaction was followed with a filter process from which a filtrate was obtained. The filtrate was condensed to a volume that was equal to ⅓ of an original volume by condensed crystallization after being supplemented for a consumed sulfuric acid. In such a condition, a crystallization rate of the phosphotungstic acid was 72.9%. After a second filter, a mother liquor was obtained; after being supplemented for phosphoric acid and the water to an original level, the mother liquor was returned for ore leaching. The phosphotungstic acid crystals were dissolved in the water to obtain a phosphotungstic acid solution having 364.7 g/L of WO3 which was then added into an ammonia solution to obtain an ammonium tungstate solution having 225.1 g/L of WO3.
While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010605094.7 | Dec 2010 | CN | national |
| 201010605095.1 | Dec 2010 | CN | national |
| 201010605103.2 | Dec 2010 | CN | national |
| 201010605107.0 | Dec 2010 | CN | national |
| 201010605110.2 | Dec 2010 | CN | national |
This application is a continuation-in-part of International Patent Application No. PCT/CN2011/001895 with an international filing date of Nov. 11, 2011, designating the United States, now pending, and further claims priority benefits to Chinese Patent Application No. 201010605094.7 filed Dec. 24, 2010, to Chinese Patent Application No. 201010605095.1 filed Dec. 24, 2010, to Chinese Patent Application No. 201010605103.2 filed Dec. 24, 2010, to Chinese Patent Application No. 201010605107.0 filed Dec. 24, 2010, and to Chinese Patent Application No. 201010605110.2 filed Dec. 24, 2010. The contents of all of the aforementioned applications, including any intervening amendments thereto, are incorporated herein by reference. Inquiries from the public to applicants or assignees concerning this document or the related applications should be directed to: Matthias Scholl P.C., Attn.: Dr. Matthias Scholl Esq., 14781 Memorial Drive, Suite 1319, Houston, Tex. 77079.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2011/001895 | Nov 2011 | US |
| Child | 13794844 | US |
