Method for recovering tungsten and molybdenum from high-fluorine high-carbon complex trace tungsten and molybdenum solution

Abstract

The invention discloses a method for recovering tungsten and molybdenum from a high-fluorine high-carbon complex trace tungsten and molybdenum solution, and belongs to the technical field of chemical metallurgy. According to the method, a conventional manganese salt reagent is introduced, tungsten-molybdenum separation is carried out in the complex trace tungsten-molybdenum solution, fluorine ions and carbonate ions contained in the solution are fixed into the tungsten-rich slag, one-step co-precipitation separation of impurities is achieved, molybdenum and tungsten in the leachate obtained from low-grade complex tungsten-molybdenum ore can be separated and recycled, and the method is suitable for industrial production. The method is a process which is simple, effective, easy to operate, easy to amplify, environment-friendly, low in cost and good in tungsten-molybdenum separation effect.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical metallurgy, and in particular relates to a method for recovering tungsten and molybdenum from a complex trace tungsten and molybdenum solution with high fluorine and high carbon. Background Art

[0002] my country is rich in molybdenum and tungsten mineral resources, and its reserves rank first in the world. Molybdenum and tungsten are important strategic metals in my country. They are widely used in military, electronics, medical and other industries because of their excellent physical and chemical properties. From the mining, mineral processing and enrichment of molybdenum and tungsten ores to the subsequent smelting, a series of physical and chemical processes are required. However, due to the extremely similar chemical properties of the two, whether it is through the separation of molybdenum and tungsten minerals from natural minerals in nature through mineral processing technology, or through the separation of molybdenum and tungsten ions in solution through chemical processes, it is often difficult to achieve efficient tungsten and molybdenum separation.

[0003] In a certain place in Henan Province, my country, there is a low-grade, difficult-to-process complex molybdenum-tungsten associated ore. The ore has special properties, with sulfide minerals and oxidized minerals coexisting. It is impossible to effectively enrich and separate tungsten and molybdenum through ore dressing methods. Therefore, patents have proposed smelting methods and treatment methods for low-grade tungsten-molybdenum ores. Patents CN118028629A and CN118529777A respectively leached low-grade tungsten-molybdenum ores through alkaline leaching and acid leaching to obtain complex trace molybdenum-tungsten leaching solutions. In this solution, C(HCO 3 - , CO 3 2- )、F、SO 4 2- , Cl and other complex ions. In addition, similar low-concentration and complex molybdenum-tungsten wastewater is also produced in the process of molybdenum and tungsten smelting. However, there are few studies on the efficient separation and enrichment of tungsten and molybdenum from complex trace molybdenum-tungsten solutions. Patent CN118291763A mentions a method for removing impurities and recovering tungsten and molybdenum from low-concentration tungsten-molybdenum solutions, but does not effectively separate tungsten and molybdenum. There are many methods for separating tungsten and molybdenum from tungsten-molybdenum mixed solutions. Among them, the methods for separating and removing tungsten from molybdenum-tungsten mixed acid salt solutions include precipitation method, adsorption method, ion exchange method, solvent extraction method, liquid membrane method, etc. In the study of using precipitation method to directly precipitate and separate tungsten from molybdenum acid salt solution, there are many precipitants used in various studies, including copper salts, nickel salts, zinc salts, cobalt salts, iron salts, manganese salts, cadmium salts, strontium salts, barium salts, calcium salts and lead salts, etc. How to choose a suitable precipitation separation agent and a suitable process, and study the method of precipitating and separating tungsten and impurities from complex trace tungsten-molybdenum solutions and recovering tungsten and molybdenum is of great significance, which is a challenge faced by the metallurgical field today. Summary of the invention

[0004] The purpose of the present invention is to provide a method for recovering tungsten and molybdenum from high-fluorine and high-carbon complex trace tungsten-molybdenum solutions, which can separate and recover molybdenum and tungsten in the leaching solution obtained from low-grade complex tungsten-molybdenum ore. The present invention is simple and effective, easy to operate and easy to scale up, environmentally friendly, low-cost, and has a good tungsten-molybdenum separation effect.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution comprises the following steps:

[0007] Step 1. Adjust the pH of the high-fluorine, high-carbon, complex trace tungsten and molybdenum solution;

[0008] Step 2. Adding a tungsten-removing and impurity-removing agent to the solution after adjusting the pH, adjusting the pH, and performing solid-liquid separation after reacting at a set temperature to obtain tungsten-rich slag and a tungsten-removing solution;

[0009] Step 3. After adding inorganic acid to the tungsten-rich slag to react, solid-liquid separation is performed to obtain tungstic acid and manganese-rich solution;

[0010] Step 4. Add a precipitant to the tungsten removal solution to enrich and recover molybdenum ions, and perform solid-liquid separation after the reaction to obtain an artificial molybdenum-rich ore.

[0011] In step 1, the high-fluorine and high-carbon complex trace tungsten-molybdenum solution is a leaching solution of a complex low-grade molybdenum-tungsten ore, which includes Mo 0.1g / L-5g / L, W 0.1g / L-5g / L, F - 0-10g / L, SO 4 2- 0-20g / L, C 0-10g / L, Cl 0-20g / L;

[0012] The pH is adjusted to pH=8-12, preferably pH=9-10.5, using an inorganic acid, sodium hydroxide or ammonia water; the inorganic acid is HCl, H 2 SO 4 or HNO 3 .

[0013] In step 2, the tungsten and impurity removal reagent is a manganese-containing reagent, including one or more of manganese chloride, manganese sulfate, and manganese nitrate; the manganese-containing reagent is a solid reagent or a solution thereof, wherein the Mn in the manganese-containing reagent solution is 2+ Concentration is 0.1mol / L~2mol / L;

[0014] The addition amount of the manganese-containing reagent is calculated based on the amount of substance of manganese as n(Mn) = a×n(W) + b×n(F) + c×n(C), where n(Mn), n(W), n(F), and n(C) are the amounts of substance of Mn, W, F, and C respectively, a = 0.5 - 3.0, b = 0.1 - 2.0, and c = 0.1 - 3.0;

[0015] The cumulative addition time of the tungsten-removing and impurity-removing reagent is 0.5 h to 4 h;

[0016] Adjust the pH to pH = 7.5 - 9.5 using inorganic acid, sodium hydroxide, or ammonia water, where the inorganic acid added is the same as the inorganic acid added in Step 1;

[0017] The reaction temperature is 25°C - 90°C, and the reaction time is 1 h to 8 h.

[0018] In Step 3, the inorganic acid is one of HCl, H 2 SO 4 、HNO 3 , which is the same as the anion of the manganese salt described in Step 2; the concentration of the inorganic acid is 1 mol / L - 5 mol / L;

[0019] The reaction temperature is 20°C - 90°C, the reaction time is 0.5 h - 8 h, and the liquid-solid ratio is (1:1) - (20:1);

[0020] In Step 3, after adjusting the pH, evaporating and concentrating, and cooling and crystallizing the manganese-rich solution, the precipitate obtained is used to prepare the tungsten-removing and impurity-removing reagent;

[0021] Or the solution obtained by evaporating and removing fluorine, adjusting the pH, and concentrating the manganese-rich solution is used as the tungsten-removing and impurity-removing reagent.

[0022] In Step 4, the precipitant is one of calcium chloride, calcium nitrate, manganese chloride, manganese sulfate, manganese nitrate, strontium chloride, strontium nitrate, lead chloride, and lead nitrate; the precipitant is a solid reagent or its solution; among them, the concentration of the precipitant solution is 0.5 mol / L - 2 mol / L; the molar ratio of the precipitant added to the molybdenum ions in the tungsten-removing solution is 0.8 - 10.0;

[0023] The cumulative addition time of the precipitant is 0.25 h to 4 h, the reaction temperature is 25°C - 90°C, and the reaction time is 1 h to 8 h.

[0024] In the method for recovering tungsten and molybdenum from a high-fluorine, high-carbon, complex, and trace tungsten-molybdenum solution, inorganic acid, manganese salt reagent, and precipitant are selected according to the impurity ions with higher ion concentrations in the process flow.

[0025] Furthermore, for the high-fluorine, high-carbon, complex trace tungsten-molybdenum solution extracted from low-grade complex tungsten-molybdenum ore, the solution adopted by the present invention is an overall solution, and the corresponding tungsten-molybdenum separation and recovery effect can only be achieved in accordance with the above process.

[0026] The beneficial effects of the present invention are as follows:

[0027] (1) The method provided by the present invention for recovering tungsten and molybdenum from a complex trace tungsten and molybdenum solution with high fluorine and high carbon is to separate tungsten and molybdenum from the complex trace tungsten and molybdenum solution by introducing a conventional manganese salt reagent, and to fix the fluoride ions and carbonate ions contained in the solution into the tungsten-rich slag, thereby realizing the one-step co-precipitation separation of impurities.

[0028] (2) The method provided by the present invention for recovering tungsten and molybdenum from a high-fluorine, high-carbon, complex trace tungsten and molybdenum solution uses reagents such as manganese chloride, manganese sulfate, calcium chloride, and sulfuric acid for precipitation separation and recovery of tungsten and molybdenum. The reagents used in the whole process are green, environmentally friendly, and low in cost, and have high economic benefits and broad application prospects.

[0029] (3) The method provided by the present invention for recovering tungsten and molybdenum from a complex trace tungsten and molybdenum solution with high fluorine and high carbon has no high temperature and pressure in the reaction process, has a good operating environment, low energy consumption, and is easy to expand the test and carry out industrialization. DETAILED DESCRIPTION

[0030] The present invention provides a method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution, wherein the high-fluorine and high-carbon complex trace tungsten and molybdenum solution is a leaching solution of a complex low-grade molybdenum and tungsten ore, and comprises, in terms of mass concentration, 0.1 g / L-5 g / L of Mo, 0.1 g / L-5 g / L of W, and 0.1 g / L-5 g / L of F. - 0-10g / L, SO 4 2- 0-20g / L, C 0-10g / L, Cl 0-20g / L. The method provided by the present invention comprises the following steps:

[0031] Step 1. Use inorganic acid, sodium hydroxide or ammonia water to adjust the pH of high-fluorine and high-carbon complex trace tungsten and molybdenum solution to pH = 8 to 12, preferably pH = 9 to 10.5; wherein the inorganic acid is HCl, H 2 SO 4 or HNO 3 ;

[0032] Step 2. Add a manganese-containing reagent as a tungsten-removing and impurity-removing reagent to the solution after adjusting the pH within 0.5h to 4h, adjust the pH to pH = 7.5 to 9.5, react at a temperature of 25°C to 90°C for 1h to 8h, and then perform solid-liquid separation to obtain tungsten-rich slag and tungsten-removing solution; wherein the manganese-containing reagent is one or more of manganese chloride, manganese sulfate, and manganese nitrate, and the manganese-containing reagent is a solid reagent or Mn 2+For a solution with a concentration of 0.1 mol / L to 2 mol / L, the amount of manganese-containing reagent added is calculated as the amount of manganese substance: n(Mn)=a×n(W)+b×n(F)+c×n(C), wherein n(Mn), n(W), n(F), and n(C) are the amounts of Mn, W, F, and C, respectively; a=0.5-3.0, b=0.1-2.0, and c=0.1-3.0;

[0033] Step 3. Add 1 mol / L-5 mol / L of inorganic acid (HCl, H 2 SO 4 , HNO 3 The liquid-to-solid ratio is (1:1) to (20:1); after reacting at 20℃-90℃ for 0.5h-8h, solid-liquid separation is performed to obtain tungstic acid and manganese-rich solution; the manganese-rich solution is adjusted to pH, evaporated and concentrated, cooled and crystallized to obtain a precipitate, which is used to prepare a tungsten removal and impurity removal agent; or the manganese-rich solution is evaporated to remove fluorine, the pH is adjusted, and the concentrated solution is used as a tungsten removal and impurity removal agent;

[0034] Step 4. Add one of calcium chloride, calcium nitrate, manganese chloride, manganese sulfate, manganese nitrate, strontium chloride, strontium nitrate, lead chloride and lead nitrate as a precipitant to the tungsten removal solution within a cumulative addition time of 0.25h to 4h to enrich and recover molybdenum ions, react at 25℃ to 90℃ for 1h to 8h, and then perform solid-liquid separation to obtain artificial rich molybdenum ore. Wherein, the precipitant is a solid reagent or a solution with a concentration of 0.5mol / L to 2mol / L, and the molar ratio of the precipitant to the molybdenum ions in the tungsten removal solution is 0.8 to 10.0.

[0035] In the method for recovering tungsten and molybdenum from a high-fluorine, high-carbon, complex trace tungsten and molybdenum solution provided by the present invention, inorganic acid, manganese salt reagent and precipitant are selected according to impurity ions with higher ion concentration in the process flow.

[0036] In the method provided by the present invention, during the separation and impurity removal of tungsten and molybdenum in step 2, manganese tungstate precipitation will be formed prior to manganese molybdate precipitation, and divalent manganese ions will combine with fluoride ions, carbonate ions and bicarbonate ions in the solution to form a co-precipitation, forming manganese fluoride, manganese carbonate and other substances that enter the artificial tungsten-rich ore;

[0037] In step 1 and step 2, the pH value before and during the reaction and the amount of manganese salt reagent added need to be strictly controlled, otherwise, it will cause negative effects such as co-precipitation of molybdenum and tungsten and low tungsten precipitation rate, poor molybdenum and tungsten separation effect.

[0038] In step 3, during the treatment of tungsten-rich slag with inorganic acid, manganese tungstate will dissolve, the manganese ions therein will enter the solution, the tungstate ions will form tungstic acid precipitates, manganese fluoride and manganese carbonate will also dissolve in the inorganic acid solution and separate from tungstic acid, and a tungstic acid intermediate product is obtained in this step.

[0039] In the method provided by the present invention, when the reagents mentioned in step 2 and step 4 are added in the form of solid reagents, they are reagents that may contain crystal water.

[0040] For the high-fluorine, high-carbon, complex trace tungsten-molybdenum solution extracted from low-grade complex tungsten-molybdenum ore, the solution adopted by the present invention is an overall solution, and the corresponding tungsten-molybdenum separation and recovery effect can only be achieved in accordance with the above process.

[0041] The specific implementation of the present invention is further described in detail below in conjunction with specific examples, which are intended to be used to explain the present invention but should not be construed as limiting the present invention.

[0042] Unless otherwise specified, the experimental reagents and materials used in the embodiments of the present invention are all commercially available.

[0043] Example 1

[0044] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 0.500g / L, W 0.19g / L, C 1.000g / L, SO 4 2- 1.200g / L, F 1.000g / L, Cl 1.44g / L, pH 12.

[0045] (1) Add concentrated hydrochloric acid to adjust the pH to 10.

[0046] (2) Add 50 mL of 1 mol / L MnCl at a constant rate of 1 mL / min. 2 The solution was reacted at 60°C for 2 hours, and the pH of the reaction was controlled between 8 and 9.5 using hydrochloric acid, NaOH or ammonia water. The artificial tungsten-rich ore and tungsten removal solution were obtained by solid-liquid separation.

[0047] (3) Add the artificial tungsten-rich ore obtained in step (2) to a 3 mol / L HCl solution, with a liquid-to-solid ratio of 4:1, a reaction temperature of 50°C, and a reaction time of 2 h. After the reaction is completed, solid-liquid separation is performed to obtain tungstic acid precipitate and manganese chloride solution. The manganese chloride solution is adjusted to pH 6.5, evaporated and concentrated, and cooled and crystallized to obtain manganese chloride crystals as a new precipitant raw material.

[0048] (4) Add 2 mol / L CaCl to the tungsten removal solution obtained in step (2) within 0.25 h. 2 The solution was added in an amount of 20 mL and reacted at 80 °C for 2 h. After the reaction, the solid and liquid were separated to obtain artificial molybdenum-rich ore.

[0049] It was determined that in step (2), the precipitation rate of tungsten was 95.97%, the loss rate of molybdenum was 6.64%, the separation coefficient was 334.82, the F removal rate was 87.51%, and the C removal rate was 79.35%. In step (4), the precipitation rate of molybdenum was 96.56%, SO 4 2- The precipitation rate was 36.19%.

[0050] Example 2

[0051] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 0.390g / L, W 0.13g / L, C 0.870g / L, SO 4 2- 1.800g / L, F 0.880g / L, pH 13.

[0052] (1) Add concentrated sulfuric acid to adjust the pH to 8.5.

[0053] (2) Add 5.5 g MnSO in three times 4 7H 2 O, the interval between each reagent addition is 20 minutes, the total reaction time is 1.5 hours at 80℃, and the reaction pH is controlled between 8-9.5 by sulfuric acid, NaOH or ammonia water during the reaction process. The artificial tungsten-rich ore and tungsten removal solution are obtained by solid-liquid separation.

[0054] (3) Add the artificial rich tungsten ore obtained in step (2) to 2 mol / L H 2 SO 4 In the solution, the liquid-solid ratio is 3:1, the reaction temperature is 80℃, and the reaction time is 3h. After the reaction, solid-liquid separation is performed to obtain tungstic acid precipitate and manganese sulfate solution. The manganese sulfate solution is adjusted to pH 5.5, evaporated and concentrated, cooled and crystallized to obtain manganese chloride crystals as a new precipitant raw material.

[0055] (4) Add 15 g ZnSO to the tungsten removal solution obtained in step (2) within 0.5 h. 4 7H 2 O, react at 90 ° C for 2h, and after the reaction, solid-liquid separation is performed to obtain artificial molybdenum-rich ore.

[0056] It was determined that in step (2), the precipitation rate of tungsten was 92.88%, the loss rate of molybdenum was 2.36%, the separation coefficient was 539.71, the F removal rate was 71.38%, and the C removal rate was 65.72%. In step (4), the precipitation rate of molybdenum was 97.25%.

[0057] Example 3

[0058] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 2.72g / L, W 1.59g / L, C 5.85g / L, F 2.37g / L, pH 7.

[0059] (1) Add sodium hydroxide solution to adjust the pH to 9.5.

[0060] (2) Add 50 mL of 1.5 mol / L MnSO at a constant rate of 0.5 mL / min. 4 The solution was reacted at 45°C for 2.5 hours, and sulfuric acid, NaOH or ammonia water were used to control the reaction pH between 8 and 9.5. The artificial tungsten-rich ore and tungsten removal solution were obtained by solid-liquid separation.

[0061] (3) Add the artificial rich tungsten ore obtained in step (2) to 3 mol / L H 2 SO 4 In the solution, the liquid-to-solid ratio is 2.5:1, the reaction temperature is 90°C, and the reaction time is 1.5h. After the reaction is completed, solid-liquid separation is performed to obtain tungstic acid precipitate and manganese sulfate solution. The manganese sulfate solution is adjusted to pH 5.5, evaporated and concentrated, and cooled and crystallized to obtain manganese sulfate crystals as a new precipitant raw material.

[0062] (4) Add 22 g of MnSO to the tungsten removal solution obtained in step (2) within 1 h. 4 ·4H 2 O, react at 80 ° C for 3 hours, and after the reaction is completed, solid-liquid separation is performed to obtain artificial molybdenum-rich ore.

[0063] The results show that in step (2), the precipitation rate of tungsten is 98.27%, the loss of molybdenum is 5.81%, the separation coefficient is 920.88, the F removal rate is 92.38%, and the C removal rate is 89.66%. In step (4), the precipitation rate of molybdenum is 97.19%.

[0064] Example 4

[0065] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 4.08g / L, W 2.49g / L, C 7.95g / L, F 3.51g / L, SO 4 2- 8.40g / L, pH=12.

[0066] (1) Add concentrated sulfuric acid to adjust the pH to 9.0.

[0067] (2) Add 8g MnSO in three times 4 ·H 2O, the interval between each reagent addition is 30 minutes, the total reaction time is 4 hours at 45℃, and the reaction pH is controlled between 8-9.5 by sulfuric acid, NaOH or ammonia water during the reaction process. The artificial tungsten-rich ore and tungsten removal solution are obtained by solid-liquid separation.

[0068] (3) Add the artificial rich tungsten ore obtained in step (2) to 1 mol / L H 2 SO 4 In the solution, the liquid-to-solid ratio is 8:1, the reaction temperature is 90°C, and the reaction time is 4.5h. After the reaction is completed, solid-liquid separation is performed to obtain tungstic acid precipitate and manganese sulfate solution. The manganese sulfate solution is adjusted to pH 6.0, evaporated and concentrated, and cooled and crystallized to obtain manganese sulfate crystals as a new precipitant raw material.

[0069] (4) Add 50 g MnSO to the tungsten removal solution obtained in step (2) within 4 h. 4 ·H 2 O, react at 25 ° C for 8 hours, and after the reaction is completed, solid-liquid separation is performed to obtain artificial molybdenum-rich ore.

[0070] The results show that in step (2), the precipitation rate of tungsten is 98.19%, the loss rate of molybdenum is 8.95%, the separation coefficient is 551.88, the F removal rate is 87.67%, and the C removal rate is 82.94%. In step (4), the precipitation rate of molybdenum is 98.83%.

[0071] Example 5

[0072] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 4.71g / L, W 4.89g / L, C 3.92g / L, SO 4 2- 15.200g / L, F 2.54g / L, Cl 17.56g / L, pH 11.

[0073] (1) Add concentrated sulfuric acid to adjust the pH to 8.5.

[0074] (2) Add 12 g MnCl in four times 2 ·4H 2 O, the interval between each reagent addition is 30 minutes, the total reaction time is 4 hours at 45℃, and the reaction pH is controlled between 8-9.5 by sulfuric acid, NaOH or ammonia water during the reaction process. The artificial tungsten-rich ore and tungsten removal solution are obtained by solid-liquid separation.

[0075] (3) Add the artificial tungsten-rich ore obtained in step (2) to a 2.5 mol / L HCl solution, with a liquid-to-solid ratio of 7:1, a reaction temperature of 90°C, and a reaction time of 4 hours. After the reaction is completed, solid-liquid separation is performed to obtain tungstic acid precipitate and manganese chloride solution. The manganese chloride solution is adjusted to pH 6.5, evaporated and concentrated, and cooled and crystallized to obtain manganese chloride crystals as a new precipitant raw material.

[0076] (4) Add 50 g of CaCl to the tungsten removal solution obtained in step (2) within 4 hours. 2 , react at 40°C for 8 hours, and after the reaction, solid-liquid separation is performed to obtain artificial molybdenum-rich ore.

[0077] The results show that in step (2), the precipitation rate of tungsten is 98.57%, the loss rate of molybdenum is 10.35%, the separation coefficient is 597.06, the F removal rate is 89.32%, and the C removal rate is 87.61%. In step (4), the precipitation rate of molybdenum is 99.14%.

[0078] Comparative Example 1

[0079] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 0.500g / L, W 0.19g / L, C 1.000g / L, SO 4 2- 1.200g / L, F 1.000g / L, Cl 1.44g / L.

[0080] The raw materials used in this comparative example are the same as those in Example 1, except that the first step (1) of adjusting the pH is not performed.

[0081] It was determined that in step (2), the precipitation rate of tungsten was 89.85%, the loss of molybdenum was 29.57%, and the separation coefficient was 21.08.

[0082] Comparative Example 2

[0083] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 0.500g / L, W 0.19g / L, C 1.000g / L, SO 4 2- 1.200g / L, F 1.000g / L, Cl 1.44g / L.

[0084] The raw materials used in this comparative example are the same as those in Example 1, except that the tungsten removal and impurity removal reagent is replaced with CaCl 2 Add in the same proportions.

[0085] It was determined that in step (2), the precipitation rate of tungsten was 97.19%, the loss of molybdenum was 58.32%, and the separation coefficient was 24.72.

[0086] Comparative Example 3

[0087] Take 1L of complex trace tungsten-molybdenum solution, which contains Mo 0.390g / L, W 0.13g / L, C 0.870g / L, SO 4 2- 1.800g / L, F 0.880g / L, pH 13.

[0088] The raw materials used in this comparative example are the same as those in Example 2, except that the reaction temperature and reaction time of step (4) are changed to 15 min at 10°C.

[0089] It was determined that in step (4), the precipitation rate of molybdenum was 55.71%.

[0090] The above are only preferred embodiments and some comparative examples of the present invention, and are not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for recovering tungsten and molybdenum from a complex trace tungsten and molybdenum solution containing high fluorine and high carbon, characterized in that: The following steps are involved: Step 1. Adjust the pH of the high-fluorine, high-carbon, complex trace tungsten and molybdenum solution; Step 2. Adding a tungsten-removing and impurity-removing agent to the solution after adjusting the pH, adjusting the pH, and performing solid-liquid separation after reacting at a set temperature to obtain tungsten-rich slag and a tungsten-removing solution; Step 3. After adding inorganic acid to the tungsten-rich slag to react, solid-liquid separation is performed to obtain tungstic acid and manganese-rich solution; Step 4. Add a precipitant to the tungsten removal solution to enrich and recover molybdenum ions, and perform solid-liquid separation after the reaction to obtain artificial molybdenum-rich ore; Wherein, in both step 1 and step 2, the pH is adjusted by using inorganic acid, sodium hydroxide or ammonia water.

2. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 1, the high-fluorine and high-carbon complex trace tungsten-molybdenum solution is a leaching solution of a complex low-grade molybdenum-tungsten ore, which includes Mo 0.1g / L-5g / L, W 0.1g / L-5g / L, F - 0-10g / L, SO4 2- 0-20g / L, C 0-10g / L, Cl 0-20g / L; The inorganic acid is HCl, H2SO4 or HNO3, and the pH is adjusted to pH = 8-12.

3. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 1, the pH is adjusted to pH = 9 to 10.

5.

4. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 2, the tungsten and impurity removal reagent is a manganese-containing reagent, including one or more of manganese chloride, manganese sulfate, and manganese nitrate; the manganese-containing reagent is a solid reagent or a solution thereof, wherein the Mn in the manganese-containing reagent solution is 2+ The concentration is 0.1mol / L~2mol / L; The cumulative addition time of tungsten removal and impurity removal reagents is 0.5h to 4h; the reaction temperature is 25℃-90℃, and the reaction time is 1h to 8h; Use inorganic acid, sodium hydroxide or ammonia water to adjust the pH to pH = 7.5-9.

5.

5. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 2, the amount of manganese-containing reagent added is calculated as the amount of manganese substance, n(Mn)=a×n(W)+b×n(F)+c×n(C), wherein n(Mn), n(W), n(F), and n(C) are the amounts of Mn, W, F, and C, respectively, a=0.5-3.0, b=0.1-2.0, and c=0.1-3.

0.

6. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 3, the inorganic acid is one of HCl, H2SO4, and HNO3, which is the same as the manganese salt anion in step 2; the concentration of the inorganic acid is 1 mol / L-5 mol / L; The reaction temperature is 20°C-90°C, the reaction time is 0.5h-8h, and the liquid-to-solid ratio is (1:1) to (20:1).

7. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 3, the manganese-rich solution is adjusted to pH, evaporated and concentrated, cooled and crystallized to obtain a precipitate, which is used to prepare a tungsten removal and impurity removal agent; Or the manganese-rich solution can be evaporated to remove fluorine, the pH value can be adjusted, and the concentrated solution can be used as a tungsten and impurity removal agent.

8. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 4, the precipitant is one of calcium chloride, calcium nitrate, manganese chloride, manganese sulfate, manganese nitrate, strontium chloride, strontium nitrate, lead chloride, and lead nitrate; the precipitant is a solid reagent or a solution thereof; wherein the concentration of the precipitant solution is 0.5 mol / L to 2 mol / L; and the molar ratio of the added precipitant to the molybdenum ions in the tungsten removal solution is 0.8 to 10.

0.

9. The method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to claim 1, characterized in that: In step 4, the cumulative addition time of the precipitant is 0.25h to 4h, the reaction temperature is 25°C to 90°C, and the reaction time is 1h to 8h.

10. A method for recovering tungsten and molybdenum from a high-fluorine and high-carbon complex trace tungsten and molybdenum solution according to any one of claims 1 to 9, characterized in that: The inorganic acid added in step 2 is the same as the inorganic acid added in step 1; The inorganic acid added in step 3 is the same as the anion of the tungsten removal and impurity removal reagent in step 2; In the method for recovering tungsten and molybdenum from complex trace tungsten and molybdenum solutions with high fluorine and high carbon content, inorganic acid, manganese salt reagent and precipitant are selected according to the impurity ions with higher ion concentration in the process flow.