CN110683582A - Method for removing phosphorus from sodium tungstate solution - Google Patents
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Abstract
The invention discloses a method for removing phosphorus from a sodium tungstate solution, wherein the sodium tungstate solution is a phosphorus-containing sodium tungstate solution produced by a tungsten smelting tungsten ore phosphate decomposition process or a sodium hydroxide-phosphate combined decomposition process, and the method comprises the following steps: (1) mixing sodium tungstate solution with calcium tungstate; (2) controlling the pH value, the temperature and the reaction time of the mixed solution in the step (1), and reacting excessive phosphate radical in the mixed solution with calcium tungstate to generate insoluble calcium phosphate precipitate under a stirring state; (3) carrying out solid-liquid separation on the solid-liquid mixture obtained in the step (2) so as to obtain low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue; (4) and using the low-phosphorus tungsten-containing filtrate to prepare a pre-mixed solution of the next ion exchange process in tungsten smelting, and returning the dephosphorization filter residue to the previous ore decomposition process to recover tungsten therein. By adopting the method, the high-efficiency separation of tungsten and phosphorus in the sodium tungstate solution can be realized, and the phosphorus removal rate is up to more than 90%.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for removing phosphorus from a sodium tungstate solution.
Background
Tungsten smelting is a dominant industry in China, and the reserves, production capacity, technical level, yield and export of metal tungsten are the first in the world. With the gradual decrease of wolframite resources, scheelite becomes a main raw material for tungsten smelting at the present stage of China. At present, the widely adopted APT production process taking tungsten ore as a raw material in China is an alkali pressure cooking-ion exchange process. In order to solve the problem that the tungsten content of the slag is higher due to the calcium return phenomenon during the alkali decomposition of the scheelite, the alkali decomposition process of the scheelite is gradually developed into a phosphate decomposition process or a sodium hydroxide-phosphate combined decomposition process. In order to allow the reaction to proceed adequately, the phosphate added is generally in excess, which results in an excess of phosphate in the sodium tungstate solution resulting from the decomposition of the ore. In order to ensure the phosphorus removal effect of the subsequent ion exchange process and the qualification of P element of an APT product obtained by final production, the method adopted by the general industrial production is to directly add calcium salt (such as calcium chloride, calcium carbonate, calcium hydroxide and the like) into a sodium tungstate solution obtained by decomposing tungsten ore for phosphorus removal, so that excessive phosphate radical in the sodium tungstate solution is removed in the form of calcium phosphate. There are several drawbacks to using this method: on one hand, a large amount of phosphorus removal reagent is consumed, and the cost is increased; on the other hand, new impurity anions are introduced into the sodium tungstate solution, which is not beneficial to subsequent ion exchange; on the other hand, in order to ensure the phosphorus removal rate, the addition coefficient of the phosphorus removal reagent is large, and certain tungsten loss is inevitably caused.
Therefore, the existing technology for removing phosphorus from sodium tungstate solution is still to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a method for removing phosphorus from a sodium tungstate solution, by adopting the method, the high-efficiency separation of tungsten and phosphorus in the sodium tungstate solution can be realized, the obtained low-phosphorus tungsten-containing filtrate can be directly used for preparing a pre-mixed solution of the next ion exchange process in tungsten smelting to prepare a qualified APT product, and the obtained tungsten-containing phosphorus removal filter residue is returned to the previous ore decomposition process to recover tungsten therein. Therefore, the method has the advantages of lower cost, higher tungsten recovery rate and the like, has no pollution to the environment, and has great popularization significance in the tungsten smelting industry.
In one aspect of the invention, the invention provides a method for removing phosphorus from a sodium tungstate solution, wherein the sodium tungstate solution is a phosphorus-containing sodium tungstate solution produced by a tungsten smelting tungsten ore phosphate decomposition process or a sodium hydroxide-phosphate combined decomposition process. According to an embodiment of the invention, the method comprises:
(1) mixing sodium tungstate solution with calcium tungstate;
(2) controlling the pH value, the temperature and the reaction time of the mixed solution in the step (1), and reacting excessive phosphate radical in the mixed solution with calcium tungstate to generate insoluble calcium phosphate precipitate under a stirring state;
(3) carrying out solid-liquid separation on the solid-liquid mixture obtained in the step (2) so as to obtain low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue;
(4) and using the low-phosphorus tungsten-containing filtrate to prepare a pre-mixed solution of the next ion exchange process in tungsten smelting, and returning the dephosphorization filter residue to the previous ore decomposition process to recover tungsten therein.
The method for removing phosphorus from sodium tungstate solution according to the embodiment of the invention is to add calcium tungstate into sodium tungstate solution, and control the pH, temperature and reaction time of the solution due to the solubility product (1.2X 10) of calcium phosphate-29) Much smaller than the solubility product of calcium tungstate (2.13X 10)-9) Thus phosphate radical (PO) in solution4 3-) Can easily react with precipitator calcium tungstate to generate calcium phosphate precipitate, and then low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue can be obtained through solid-liquid separation, namely effective separation of tungsten and phosphorus in sodium tungstate solution is realized, and the method can basically realize complete recoveryThe excessive phosphate radical in the phosphorus-containing sodium tungstate solution reduces the phosphate consumption of ore decomposition, can reduce the tungsten loss generated by removing phosphorus by adopting common calcium salt, avoids introducing new impurity anions into the sodium tungstate solution, can directly prepare pre-delivery liquid of the next ion exchange procedure in tungsten smelting from low-phosphorus tungsten-containing filtrate, and returns the obtained tungsten-containing phosphorus-removing filter residue to the previous ore decomposition procedure to recover tungsten therein, so the method has the advantages of lower cost, higher tungsten recovery rate and the like, has no pollution to the environment, and has great popularization significance in the tungsten smelting industry.
In addition, the method for removing phosphorus in the sodium tungstate solution with high efficiency and low cost according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in step (1), the sodium tungstate solution contains sodium tungstate, sodium phosphate, and sodium hydroxide.
In some embodiments of the invention, in the step (1), the mass concentration of the P element in the sodium tungstate solution is 0.5-5 g/L, and the P element and WO are mixed3Has a mass ratio of 2X 10-3～100×10-3。
In some embodiments of the invention, in step (1), the ratio of the addition amount of the calcium tungstate to the molar mass of the P-containing element in the sodium tungstate solution is 1.0 to 5.0 times, preferably 1.2 to 4.0 times, and more preferably 1.5 to 3.0 times. Therefore, the precipitation efficiency of phosphate radicals in the sodium tungstate solution can be improved.
In some embodiments of the invention, in step (1), the calcium tungstate is obtained by evaporating mother liquor to precipitate and recover tungsten in a tungsten smelting process or is obtained commercially. Therefore, the precipitation efficiency of phosphate radicals in the sodium tungstate solution can be improved.
In some embodiments of the present invention, in the step (2), the pH value of the mixed solution is in a range of 7 to 14, preferably 9 to 14, and more preferably 9 to 12. Therefore, the precipitation efficiency of phosphate radicals in the sodium tungstate solution can be improved.
In some embodiments of the present invention, in the step (2), the temperature of the mixed solution is 20 to 100 ℃, preferably 50 to 100 ℃, and more preferably 50 to 80 ℃. Therefore, the precipitation efficiency of phosphate radicals in the sodium tungstate solution can be improved.
In some embodiments of the present invention, in the step (2), the reaction time is 0.1 to 4 hours, preferably 0.5 to 4 hours, and more preferably 0.5 to 2 hours. Therefore, the precipitation efficiency of phosphate radicals in the sodium tungstate solution can be improved.
In some embodiments of the invention, in step (3), the mass concentration of the P element in the low-phosphorus tungsten-containing filtrate is not higher than 0.1 g/L.
In some embodiments of the invention, in step (4), the element P in the pre-mix solution and WO in the sodium tungstate solution3Is not higher than 1 x 10-3. Thus, an acceptable APT can be obtained.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a process for removing phosphorus from a sodium tungstate solution according to one embodiment of the invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a method for removing phosphorus from a sodium tungstate solution is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing sodium tungstate solution with calcium tungstate
In this step, a sodium tungstate solution is mixed with calcium tungstate (artificial scheelite). Specifically, the sodium tungstate solution is produced by a tungsten smelting tungsten ore phosphate decomposition process or a sodium hydroxide-phosphate combined decomposition processThe obtained phosphorus-containing sodium tungstate solution mainly contains sodium tungstate, sodium phosphate and sodium hydroxide, and calcium tungstate is added into the sodium tungstate solution. Wherein the mass concentration of the P element is 0.5-5 g/L, such as 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1.0g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L, 2.0g/L … … 4.5.5 g/L, 4.6g/L, 4.7g/L, 4.8g/L, 4.9g/L, 5.0 g/L; p element and WO in sodium tungstate solution3Has a mass ratio of 2X 10-3～100×10-3E.g. 2 x 10-3、3×10-3、4×10-3、5×10-3、6×10-3、7×10-3、8×10-3、9×10-3、10×10-3……、95×10-3、96×10-3、97×10-3、98×10-3、99×10-3、100×10-3. The inventors have found that the solubility product of calcium phosphate is (1.2X 10)-29) Much smaller than the solubility product of calcium tungstate (2.13X 10)-9) Thus phosphate radical (PO) in solution with the addition of calcium tungstate4 3-) The calcium phosphate precipitate is easily generated by reaction with a precipitator of calcium tungstate, so that low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue can be obtained by solid-liquid separation, namely, the separation of tungsten and phosphorus is realized.
According to one embodiment of the invention, the ratio of the addition amount of the additive calcium tungstate to the molar mass of the P element contained in the solution is 1.0-5.0 times. The inventor finds that when the addition amount of the calcium tungstate additive is too low, phosphate radical is incompletely precipitated, the concentration of P in the filtrate is higher, and the addition coefficient of the additive is properly increased, so that the precipitation rate of the phosphate radical in the solution is favorably improved; however, when the addition amount of the additive exceeds a certain range, the precipitation rate of phosphate radical hardly changes, and the treatment amount of the filter residue containing tungsten and phosphorus is increased. Therefore, the amount of calcium tungstate added is preferably 1.2 to 4.0 times, and more preferably 1.5 to 3.0 times.
It should be noted that, in the present application, if not specifically stated, the calcium tungstate used may be obtained by recovering the evaporated mother liquor from the tungsten smelting process (i.e., the phosphate decomposition process of tungsten smelting ore or the combined decomposition process of sodium hydroxide and phosphate) or may be obtained by direct outsourcing. (how to precipitate and recycle the evaporation mother liquor into calcium tungstate is clear to those skilled in the tungsten smelting industry, and relevant information is easy to obtain and is not particularly described herein).
S200: controlling the pH value, the temperature and the reaction time of the mixed solution in the step S100, and enabling excessive phosphate radicals in the mixed solution to react with calcium tungstate to generate insoluble calcium phosphate precipitate in a stirring state
In this step, the pH value, reaction temperature and reaction time of the solution obtained in the above step are controlled, and stirring is carried out due to the solubility product of calcium phosphate (1.2X 10)-29) Much smaller than the solubility product of calcium tungstate (2.13X 10)-9) Thus phosphate radical (PO) in solution with the addition of calcium tungstate4 3-) Reacts with precipitator calcium tungstate to generate insoluble calcium phosphate precipitate.
According to one embodiment of the invention, the pH value of the mixed solution is in a range of 7-14. The inventor finds that when the pH value is too low, phosphate radical is not completely precipitated, so that the concentration of P contained in the filtrate after subsequent solid-liquid separation is higher; when the pH value is too high, the change of the phosphate radical precipitation rate is not obvious, and the waste of residual alkali is caused, which is not favorable for the next ion exchange process. Therefore, the pH value is preferably 9 to 14, more preferably 9 to 12.
According to another embodiment of the present invention, in the step, the reaction temperature is 20 to 100 ℃ and the reaction time is 0.1 to 4 hours. The inventor finds that in a certain temperature range, the higher the temperature is, the higher the precipitation rate of phosphate in the solution is, but the precipitation rate hardly changes after a certain temperature is exceeded; similarly, it is advantageous to increase the precipitation rate of phosphate in the solution by increasing the reaction time, but the precipitation rate hardly changes after a certain time. Such as reaction temperature of 30 degrees Celsius, 32 degrees Celsius, 35 degrees Celsius, 37 degrees Celsius, 40 degrees Celsius, 42 degrees Celsius, 45 degrees Celsius, 47 degrees Celsius, 50 degrees Celsius, 52 degrees Celsius, 55 degrees Celsius, 58 degrees Celsius, 60 degrees Celsius, 62 degrees Celsius, 65 degrees Celsius, 67 degrees Celsius, 70 degrees Celsius, 72 degrees Celsius, 75 degrees Celsius, 78 degrees Celsius, 80 degrees Celsius, 82 degrees Celsius, 85 degrees Celsius, 87 degrees Celsius, 90 degrees Celsius, 92 degrees Celsius, 95 degrees Celsius, 97 degrees Celsius, 100 degrees Celsius, preferably 50 to 100 degrees Celsius, more preferably 50 to 80 degrees Celsius, for example, the reaction is stirred for 0.5 hours, 0.7 hours, 1.0 hour, 1.2 hours, 1.5 hours, 1.7 hours, 2.0 hours, 2.2 hours, 2.5 hours, 2.7 hours, 3.0 hours, 3.2 hours, 3.5 hours, 3.7 hours, 4.0 hours, 4.5 hours, 2.5 hours, 2.7 hours, 3.0 hours, 3.5 hours, 3.7 hours, 3.5, 5.5 hours, 5.7 hours, 6.0 hours, preferably 0.5 to 4 hours, more preferably 0.5 to 2 hours.
S300: carrying out solid-liquid separation on the solid-liquid mixture
In the step, the obtained solid-liquid mixture is subjected to solid-liquid separation to obtain low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue. Specifically, the mass concentration of the P element in the obtained low-phosphorus tungsten-containing filtrate is not higher than 0.1g/L, and the phosphorus removal rate can reach more than 90%.
S400: the low-phosphorus tungsten-containing filtrate is used for preparing a pre-mixed solution of the next ion exchange procedure of tungsten smelting, and the dephosphorization filter residue is returned to the previous ore decomposition procedure to recover tungsten therein
In the step, the low-phosphorus tungsten-containing filtrate obtained in the step is directly used for preparing a pre-mixing liquid of the next ion exchange process in tungsten smelting, and the obtained tungsten-containing phosphorus-removing filter residue is returned to the previous ore decomposition process (namely the tungsten smelting tungsten ore phosphate decomposition process or the sodium hydroxide-phosphate combined decomposition process) to recycle tungsten therein, so that the recovery rate of metal tungsten is improved. Therefore, phosphorus is removed from the sodium tungstate solution by the method, any phosphorus removal reagent is not required to be additionally consumed, and the excessive phosphate radical in the sodium phosphotungstate solution can be completely utilized and used for decomposing calcium tungstate, so that the loss of the phosphate radical is avoided, and the cost is lower. In addition, by removing phosphorus from the sodium tungstate solution by the method, the tungsten loss can be reduced, and the recovery rate of metal tungsten is improved. In addition, the method for removing phosphorus from the sodium tungstate solution does not introduce new impurity anions into the sodium tungstate solution, and is favorable for subsequent ion exchange. Preferably, the element P in the pre-crosslinking solution and the WO in the sodium tungstate solution3Is not higher than 1 x 10-3Thereby ensuring that the P element which can be produced is qualifiedThe APT product of (1).
It should be noted that, in the method of the present application, the steps such as feeding, filtering, and preparing the pre-mix solution of the next ion exchange process in tungsten smelting may be the same as those in the prior art, and those skilled in the art can know that the description is omitted here.
The method for removing phosphorus from sodium tungstate solution according to the embodiment of the invention is to add calcium tungstate into sodium tungstate solution, and control the pH, temperature and reaction time of the solution due to the solubility product (1.2X 10) of calcium phosphate-29) Much smaller than the solubility product of calcium tungstate (2.13X 10)-9) Thus phosphate radical (PO) in solution4 3-) Can easily react with precipitator calcium tungstate to generate calcium phosphate precipitate, and then low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue can be obtained through solid-liquid separation, namely, the effective separation of tungsten and phosphorus in the sodium tungstate solution is realized, and the method can basically realize the complete recovery of excessive phosphate radical in the sodium tungstate solution containing phosphorus, reduce the phosphate consumption of ore decomposition, reduce the tungsten loss generated by phosphorus removal by adopting common calcium salt, but also avoids introducing new impurity anions into the sodium tungstate solution, the obtained low-phosphorus tungsten-containing filtrate can be directly used for preparing pre-mixed liquor of the next ion exchange procedure in tungsten smelting, and the obtained tungsten-containing phosphorus removal filter residue is returned to the previous ore decomposition procedure to recover tungsten therein, therefore, the method has the advantages of lower cost, higher tungsten recovery rate and the like, has no pollution to the environment, and has great popularization significance in the tungsten smelting industry.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Taking 1L of phosphorus-containing sodium tungstate solution obtained by tungsten ore sodium hydroxide-phosphate combined decomposition process in industrial production practice, and adding WO in the solution3The concentration is 120g/L, the mass concentration of the P element is 1g/L, and the P element and WO in sodium tungstate3Has a mass ratio of 8.3X 10-3；
(2) The mixed solution had an initial pH of 14 and was slowly added while stirring21.7g WO3Calcium tungstate (theoretical amount is 1.5 times) with the content of 65 percent and the water content of 1 weight percent is heated to 60 ℃ and stirred for reaction for 1 hour;
(3) filtering the solid-liquid mixture obtained in the step (2) to obtain a low-phosphorus tungsten-containing solution and a tungsten-containing phosphorus removal filter residue, wherein the volume of the low-phosphorus tungsten-containing solution is about 0.95L, and the WO in the low-phosphorus tungsten-containing solution is detected3The concentration is 115g/L, the mass concentration of the P element is 0.08g/L, and the P element and WO in sodium tungstate3Is 0.7X 10-3The phosphorus removal rate reaches 92.4 percent. The content of the P element in the obtained low-phosphorus sodium tungstate solution meets the standard of preparing pre-mixed solution in the next ion exchange process, qualified APT products can be produced, the obtained tungsten-containing dephosphorization filter residue is returned to the previous ore decomposition process to recover tungsten in the filter residue, the tungsten loss is reduced, and the recovery rate of metal tungsten is improved.
Example 2
(1) Taking 1L of phosphorus-containing sodium tungstate solution obtained by tungsten ore sodium hydroxide-phosphate combined decomposition process in industrial production practice, and adding WO in the solution3The concentration is 128g/L, the mass concentration of the P element is 2.5g/L, and the P element and WO in sodium tungstate3Has a mass ratio of 19.5X 10-3；
(2) The initial pH of the mixed solution was 13, and 57.7g of WO was added3Calcium tungstate (theoretical amount 1.6 times) with the content of 65% and the water content of 1 wt% is heated to 50 ℃, and stirred for reaction for 0.5 h;
(3) filtering the solid-liquid mixture obtained in the step (2) to obtain a low-phosphorus tungsten-containing solution and a tungsten-containing phosphorus removal filter residue, wherein the volume of the low-phosphorus tungsten-containing solution is about 0.90L, and the WO in the low-phosphorus tungsten-containing solution is detected3The concentration is 120g/L, the mass concentration of the P element is 0.1g/L, and the P element and WO in sodium tungstate3Is 0.8X 10-3The phosphorus removal rate reaches 91 percent. The content of the P element in the obtained low-phosphorus sodium tungstate solution meets the standard of preparing pre-mixed solution in the next ion exchange process, qualified APT products can be produced, the obtained tungsten-containing dephosphorization filter residue is returned to the previous ore decomposition process to recover tungsten in the filter residue, the tungsten loss is reduced, and the recovery rate of metal tungsten is improved.
Example 3
(1) Taking sodium hydroxide-phosphate of tungsten ore in industrial production practice1L of sodium phosphotungstate solution obtained by combined decomposition process, WO in the solution3The concentration is 150g/L, the mass concentration of the P element is 1g/L, and the P element and WO in sodium tungstate3Has a mass ratio of 6.7X 10-3；
(2) The mixed solution had an initial pH of 10, and 24.5g of WO was slowly added thereto under stirring3Calcium tungstate (theoretical amount 1.7 times) with the content of 65% and the water content of 1 wt% is heated to 70 ℃, and stirred to react for 1.5 hours;
(3) filtering the solid-liquid mixture obtained in the step (2) to obtain a low-phosphorus tungsten-containing solution and a tungsten-containing phosphorus removal filter residue, wherein the volume of the low-phosphorus tungsten-containing solution is about 0.94L, and the WO in the low-phosphorus tungsten-containing solution is detected3The concentration is 138g/L, the mass concentration of the P element is 0.07g/L, and the P element and WO in sodium tungstate3Is 0.5X 10-3The phosphorus removal rate reaches 93.4 percent. The content of the P element in the obtained low-phosphorus sodium tungstate solution meets the standard of preparing pre-mixed solution in the next ion exchange process, qualified APT products can be produced, the obtained tungsten-containing dephosphorization filter residue is returned to the previous ore decomposition process to recover tungsten in the filter residue, the tungsten loss is reduced, and the recovery rate of metal tungsten is improved.
Example 4
(1) Taking 1L of phosphorus-containing sodium tungstate solution obtained by tungsten ore sodium hydroxide-phosphate combined decomposition process in industrial production practice, and adding WO in the solution3The concentration is 90g/L, the mass concentration of the P element is 1.2g/L, and the P element and WO in sodium tungstate3Has a mass ratio of 13.3X 10-3；
(2) The mixed solution had an initial pH of 14, and 34.6g of WO was slowly added thereto with stirring3Calcium tungstate (2.0 times of theoretical amount) with the content of 65 percent and the water content of 1 weight percent is heated to 80 ℃ and stirred for reaction for 2 hours;
(3) filtering the solid-liquid mixture obtained in the step (2) to obtain a low-phosphorus tungsten-containing solution and a tungsten-containing phosphorus removal filter residue, wherein the volume of the low-phosphorus tungsten-containing solution is about 0.96L, and the WO in the low-phosphorus tungsten-containing solution is detected3The concentration is 87g/L, the mass concentration of the P element is 0.06g/L, and the P element and WO in sodium tungstate3Is 0.7X 10-3The phosphorus removal rate reaches 94.2 percent. The content of the P element of the obtained low-phosphorus sodium tungstate solution meets the requirement of preparing the next ion exchange procedureThe standard of the former liquid can produce qualified APT products, and the obtained tungsten-containing dephosphorization filter residue is returned to the former ore decomposition procedure to recover tungsten therein, thereby reducing tungsten loss and improving the recovery rate of metal tungsten.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for removing phosphorus from a sodium tungstate solution, wherein the sodium tungstate solution is a phosphorus-containing sodium tungstate solution produced by a tungsten smelting tungsten ore phosphate decomposition process or a sodium hydroxide-phosphate combined decomposition process, and the method comprises the following steps:
(1) mixing sodium tungstate solution with calcium tungstate;
(2) controlling the pH value, the temperature and the reaction time of the mixed solution in the step (1), and reacting excessive phosphate radical in the mixed solution with calcium tungstate to generate insoluble calcium phosphate precipitate under a stirring state;
(3) carrying out solid-liquid separation on the solid-liquid mixture obtained in the step (2) so as to obtain low-phosphorus tungsten-containing filtrate and tungsten-containing phosphorus-removing filter residue;
(4) and using the low-phosphorus tungsten-containing filtrate to prepare a pre-mixed solution of the next ion exchange process in tungsten smelting, and returning the dephosphorization filter residue to the previous ore decomposition process to recover tungsten therein.
2. The method according to claim 1, wherein in step (1), the sodium tungstate solution contains sodium tungstate, sodium phosphate, and sodium hydroxide.
3. The method according to claim 1, wherein in the step (1), the mass concentration of the P element in the sodium tungstate solution is 0.5-5 g/L, and the P element and WO are mixed3Has a mass ratio of 2X 10-3～100×10-3。
4. A method according to any one of claims 1 to 3, wherein in step (1), the ratio of the addition amount of the calcium tungstate to the molar mass of the P element in the sodium tungstate solution is 1.0 to 5.0 times, preferably 1.2 to 4.0 times, and more preferably 1.5 to 3.0 times.
5. The method according to claim 1, wherein in the step (1), the calcium tungstate is obtained by evaporating mother liquor to precipitate and recover tungsten in a tungsten smelting process or is obtained commercially.
6. The method according to claim 1, wherein in the step (2), the pH value of the mixed solution is in the range of 7 to 14, preferably 9 to 14, and more preferably 9 to 12.
7. The method according to claim 1 or 6, wherein the temperature of the mixed solution in the step (2) is 20 to 100 ℃, preferably 50 to 100 ℃, and more preferably 50 to 80 ℃.
8. The method according to claim 1, wherein in step (2), the reaction time is 0.1 to 4 hours, preferably 0.5 to 4 hours, and more preferably 0.5 to 2 hours.
9. The method according to claim 1, wherein in the step (3), the mass concentration of the P element in the low-phosphorus tungsten-containing filtrate is not higher than 0.1 g/L.
10. The method of claim 1, wherein in step (4), the P element in the pre-mix solution and WO in the sodium tungstate solution3Is not higher than 1 x 10-3。
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| CN102134099A (en) * | 2011-01-30 | 2011-07-27 | 湖南辰州矿业股份有限公司 | Deep purification and phosphorus removal method for mixed liquor of coarse sodium tungstate solution and crystallized mother liquor |
| CN104310483A (en) * | 2014-09-25 | 2015-01-28 | 江西稀有稀土金属钨业集团有限公司 | Method for deeply removing phosphorus in coarse sodium tungstate solution |
| CN107522232A (en) * | 2017-09-18 | 2017-12-29 | 江西理工大学 | Tungsten, the method for phosphorus separation in a kind of Tungsten smelting sodium tungstate solution |
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| CN102134099A (en) * | 2011-01-30 | 2011-07-27 | 湖南辰州矿业股份有限公司 | Deep purification and phosphorus removal method for mixed liquor of coarse sodium tungstate solution and crystallized mother liquor |
| CN104310483A (en) * | 2014-09-25 | 2015-01-28 | 江西稀有稀土金属钨业集团有限公司 | Method for deeply removing phosphorus in coarse sodium tungstate solution |
| CN107522232A (en) * | 2017-09-18 | 2017-12-29 | 江西理工大学 | Tungsten, the method for phosphorus separation in a kind of Tungsten smelting sodium tungstate solution |
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