CN110904350B - Method for separating tungsten and molybdenum - Google Patents
Method for separating tungsten and molybdenum Download PDFInfo
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Abstract
The invention relates to a method for separating tungsten and molybdenum, and belongs to the technical field of tungsten and molybdenum extraction. The method for separating tungsten and molybdenum provided by the invention comprises the following steps: using [ A336]+Or [66614]+And [ DODDGA ]]‑Or [ D ]2EHDDGA]‑The etheramide ionic liquid has the characteristic of high selectivity performance on tungsten under the condition that the pH value is 5.5-7.5, the organic phase containing the etheramide ionic liquid and the diluent is adopted to extract and separate the tungsten-molybdenum mixed solution with the pH value of 5.5-7.5, the tungsten is extracted into the organic phase, and the molybdenum is left in the raffinate, so that the separation of the tungsten and the molybdenum is realized. The method has the advantages of simple process, easy implementation and good tungsten-molybdenum separation effect, and is suitable for deep separation of tungsten and molybdenum in a macroscopic quantity of tungsten-molybdenum solution.
Description
Technical Field
The invention relates to a method for separating tungsten and molybdenum, and belongs to the technical field of tungsten and molybdenum extraction.
Background
Tungsten and molybdenum are important strategic minerals in China, and tungsten, molybdenum and tungsten-molybdenum alloys are widely used in the fields of electronic and power equipment manufacturing industry, metal material processing industry, high-temperature furnace part structure part manufacturing, aerospace, national defense industry and the like due to the characteristics of good heat conduction, electric conduction, low thermal expansion coefficient, high-temperature strength, wear resistance and the like. China has abundant tungsten and molybdenum resources, but with the development of high-quality tungsten and molybdenum mineral resources, the development and utilization of complex tungsten and molybdenum symbiotic resources are concerned by people. For example, more than 70% of tungsten ore resources in China are difficult to utilize, and the tungsten ore resources are low in grade and high in molybdenum content as associated elements.
Tungsten and molybdenum are impurity elements which are strictly controlled in tungsten and molybdenum metallurgical products respectively, however, the chemical properties of tungsten and molybdenum are similar, so that the separation of tungsten and molybdenum is difficult, and the efficient separation of tungsten and molybdenum is always a great problem in the tungsten and molybdenum metallurgical industry. With the development of tungsten-molybdenum smelting industry, scheelite with high molybdenum content gradually becomes a main raw material in tungsten smelting production, and together with the requirement of comprehensively recovering tungsten-molybdenum secondary resources (molybdenum-containing waste catalysts, molybdenum-removing slag generated by tungsten smelting enterprises, molybdenite ore dressing tailings and the like) with equivalent tungsten-molybdenum content, macro tungsten-molybdenum feed liquid is more and more common in tungsten smelting industry. The traditional method for removing trace molybdenum cannot well treat the feed liquid, for example, the problem of deep molybdenum removal in tungstate solution is solved by a selective precipitation molybdenum removal process, but the technology is suitable for treating the feed liquid with the molybdenum-tungsten molar ratio of less than 1/20, and if the molybdenum content is more than 1/20, the molybdenum removal effect is reduced, the cost of a precipitator is greatly increased, and the like. Therefore, a new method and a new technology for efficiently separating the macro tungsten and the macro molybdenum are urgently needed in the field of tungsten and molybdenum metallurgy.
In recent years, research on macro-quantity tungsten-molybdenum separation is widely focused, and Chinese patent CN102329962A discloses a method for deeply separating tungsten and molybdenum from a high-tungsten high-molybdenum mixed solution, wherein macroporous weak-alkaline anion exchange resins D301, D314 and D354 are adopted to separate tungsten and molybdenum from the high-tungsten high-molybdenum mixed solution, the deep separation of tungsten and molybdenum is realized by increasing the height of an ion exchange zone in an ion exchange column and prolonging the contact time, but the increase of the height of the ion exchange zone in the ion exchange column and the prolongation of the contact time increase the resin dosage and reduce the resin utilization efficiency. Chinese patent CN105200246A discloses a method for separating tungsten and molybdenum, which comprises, firstly, adjusting acidity, realizing tungsten and molybdenum coprecipitation under acidic condition, then mixing tungsten and molybdenum precipitates, dissolving with hydrogen peroxide and acid, adding tungsten powder under heating condition to form tungstic acid precipitate and separating molybdenum, and finally further purifying molybdenum by extraction method/ion exchange method, which is more suitable for separating high concentration tungsten and molybdenum solution. Chinese patent CN101880780A discloses a method for separating and extracting tungsten and molybdenum from a tungsten molybdate mixed solution, which adopts the idea of artificial scheelite to add calcium carbonate with the stoichiometric number being 5 times of that of the tungsten and molybdenum mixed solution, and the tungsten is precipitated into calcium tungstate under the stirring at 90 ℃ to realize the separation from the molybdenum. The extraction of tungsten from the artificial scheelite firstly obtains the artificial white tungstic acid under the conditions of stirring at 70 ℃ and 3 times of the stoichiometric hydrochloric acid, and the artificial white tungstic acid is dissolved in ammonia and evaporated to obtain the ammonium paratungstate. The method needs to decompose tungsten which is originally in the solution again after precipitation, and the whole process has higher cost. Chinese patent CN102876906A discloses a method for extracting and separating tungsten and molybdenum from a tungsten and molybdenum mixed solution, which adopts a mixture of trialkyl phosphorus oxide and tributyl phosphate as an extracting agent to extract and separate tungsten and molybdenum, but the pH value of a water phase needs to be adjusted to 3.5 before extraction, and hydrogen peroxide with the molar weight 1.5 times that of tungsten and molybdenum is added, so that the problem of high cost still exists. Therefore, the development of new high-efficiency tungsten-molybdenum separation technology is still necessary.
Disclosure of Invention
The invention aims to provide a method for separating tungsten and molybdenum, which can quickly, simply and conveniently separate tungsten and molybdenum in a tungsten-molybdenum solution and is suitable for deep separation of tungsten and molybdenum in a macroscopic quantity of tungsten-molybdenum solution.
The technical scheme of the invention is as follows:
a method for separating tungsten and molybdenum, comprising the steps of:
extracting tungsten in a tungsten-molybdenum mixed solution with the pH of 5.5-7.5 by using an organic phase containing etheramide ionic liquid and a diluent, wherein the tungsten is extracted into the organic phase, and the molybdenum is left in a raffinate, so that the separation of the tungsten and the molybdenum is realized;
the cation in the ether amide ionic liquid is [ A336]]+Or [ P66614]]+(ii) a The anion in the ether amide ionic liquid is [ DODDGA ]]-Or [ D ]2EHDDGA]-。
The method for separating tungsten and molybdenum adopts tungsten in a tungsten and molybdenum mixed solution containing etheramide ionic liquid and diluent and having an organic relative pH value of 5.5-7.5 to extract tungsten, and utilizes [ A336]]And/or [ A66614]And [ DODDGA ]]And/or [ D2EHDDGA]The etheramide ionic liquid has the characteristic of high selectivity to tungsten under the condition that the pH value is 5.5-7.5, so that tungsten is extracted into an organic phase, molybdenum is remained in raffinate, and the separation of tungsten and molybdenum is realizedThe method has the advantages of simple process, easy implementation and good tungsten-molybdenum separation effect, and is suitable for deep separation of tungsten and molybdenum in a macroscopic quantity of tungsten-molybdenum solution.
The existing tungsten-molybdenum mixed solution is generally prepared by an alkali decomposition method, so that the obtained tungsten-molybdenum mixed solution is alkaline and is an aqueous solution containing tungsten and molybdenum, and can be called an aqueous phase. The tungsten-molybdenum mixed solution can also be called a tungsten-molybdenum mixed aqueous solution. Tungsten and molybdenum in the tungsten-molybdenum mixed solution exist in the form of tungstic acid and molybdic acid respectively.
It can be understood that the pH of the tungsten-molybdenum mixed solution with the pH of 5.5 to 7.5 can be adjusted by adding acid or alkali, but the pH can be adjusted to a range of 5.5 to 7.5 by adding acid, considering that most of the existing tungsten-molybdenum mixed solutions are alkaline. The acid may be hydrochloric acid, sulfuric acid, nitric acid, or the like.
The specific operation mode of extraction is not limited, and the conventional operation mode in the field is adopted, and the extraction can be carried out by contacting an organic phase (an organic phase containing the etheramide ionic liquid and the diluent) with an aqueous phase (a tungsten-molybdenum mixed solution), and the contacting can be in a vibration mode and the like.
The cation in the etheramide ionic liquid is [ A336]]+Or [ P66614]]+(ii) a The anion in the ether amide ionic liquid is [ DODDGA ]]-Or [ D ]2EHDDGA]-. That is, the etheramide ionic liquid may be [ A336]][DODDGA]、[P66614][DODDGA]、[A336][D2EHDDGA]、[P66614][D2EHDDGA]Or a mixture thereof. The etheramide ionic liquid can be prepared according to the preparation method disclosed in the prior art, such as the synthesis by using the functional ionic liquid preparation method reported in the literature (AICHE J.2010,56: 989-996).
From [ A336]+Or [ P66614]]+Cation and [ DODDGA ]]-Or [ D ]2EHDDGA]-The etheramide ionic liquid composed of anions has high selectivity on tungsten under the condition that the pH value is 5.5-7.5, and can realize high-efficiency separation of tungsten and molybdenum, and preferably, the concentration of the etheramide ionic liquid in an organic phase is 0.05-1 mol/L.
The method for separating tungsten and molybdenum is suitable for deep separation of tungsten and molybdenum in a macroscopic quantity of tungsten and molybdenum solution, has a wide application range, and preferably, the method is suitable for deep separation of tungsten and molybdenum in a macroscopic quantity of tungsten and molybdenum solutionWO in tungsten-molybdenum mixed solution3The concentration of (B) is 1g/L to 50 g/L. I.e. for treating WO3The concentration of the tungsten and the molybdenum in the tungsten-molybdenum mixed solution is 1 g/L-50 g/L.
Preferably, in the tungsten-molybdenum mixed solution, WO3The mass ratio of the Mo to the WO is 1: 20-20: 13The sum of the Mo concentration and the Mo concentration is less than 100 g/L. The method is applicable to, WO3The mass ratio of the Mo to the WO is 1: 20-20: 13And separating tungsten and molybdenum from the tungsten-molybdenum mixed solution with the concentration sum of Mo being less than 100 g/L.
Preferably, in the tungsten-molybdenum mixed solution, WO3The mass ratio of the Mo to the WO is 3: 1-1: 103The sum of the Mo concentration and the Mo concentration is less than 90 g/L.
To further enhance the separation of tungsten and molybdenum, preferably, the organic phase further comprises isooctyl alcohol; the volume fraction of the isooctyl alcohol is 5-10%. The isooctyl alcohol is beneficial to promoting the separation of an organic phase (the organic phase containing the etheramide ionic liquid and the diluent) and a water phase (the tungsten-molybdenum mixed solution), the condition that two phases are miscible and are not easy to separate near a contact interface of the two phases is relieved, and the separation efficiency of tungsten and molybdenum is further improved.
Preferably, the diluent is sulfonated kerosene, No. 260 mineral spirits, jet fuel, n-heptane, or cyclohexane. The diluent acts as an organic phase in which the etheramide ionic liquid is soluble, thereby extracting the tungsten into the organic phase.
In order to further improve the separation efficiency, and to take account of the usage amount of the organic phase and to control the cost, the volume ratio of the organic phase to the tungsten-molybdenum mixed solution is preferably 1/2-2/1.
In order to further improve the purity of tungsten and realize cost reduction, preferably, the method for separating tungsten and molybdenum further comprises: and (3) performing back extraction on the tungsten extracted into the organic phase by using an alkaline solution as a back extraction solution to obtain a back extraction solution containing tungsten. The alkaline strip liquor is used for strip extraction of tungsten, so that the purity of tungsten can be further improved, and the stripped organic phase can be recycled.
Preferably, the organic phase subjected to stripping of the stripping solution is washed and recycled. Can be recycled after washing, and effectively reduces the cost. The washing can be carried out by water washing to remove alkali in the organic phase.
Preferably, the alkali in the alkaline solution is sodium hydroxide, ammonia water, ammonium bicarbonate, sodium carbonate or sodium bicarbonate, and the concentration of the alkali in the alkaline solution is 0.1-1.5 mol/L.
In order to further improve the separation efficiency and take account of the usage amount of the alkaline solution, the volume ratio of the alkaline solution to the organic phase is preferably 1/2-2/1.
Drawings
FIG. 1 is a structural formula of an ether amide ionic liquid.
Detailed Description
The present invention will be further described with reference to the following embodiments.
In the examples of the present invention, the ether amide ionic liquid used consists of four types: [ A336][DODDGA]、[P66614][DODDGA]、[A336][D2EHDDGA]、[P66614][D2EHDDGA]The structural formulas of the four ether amide ionic liquids are shown in figure 1.
The raw material tungsten-molybdenum mixed solution in the embodiment of the invention is an aqueous solution containing tungstic acid and molybdic acid.
In the examples of the present invention, ICP-AES was used to treat WO in the raffinate containing molybdenum and the strip liquor containing tungsten3And Mo content.
The specific embodiment of the method for separating tungsten and molybdenum of the invention is as follows:
example 1
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.5, and the pH was adjusted to 6.0 with sulfuric acid, wherein WO was contained in the tungsten-molybdenum mixed solution3And the concentration of Mo is: WO310g/L of Mo and 10g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ DODDGA ] is 0.2mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) taking 1.0mol/L sodium hydroxide as stripping solution, performing stripping on tungsten in the tungsten-containing organic phase obtained in the step (2), wherein the ratio of the stripping solution to the organic phase is 1:1, the stripping time is 3 minutes, the stripping stage number is 1 stage, after stripping, the tungsten enters the stripping solution (aqueous phase), the stripping solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing stripping solution, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: for the molybdenum-containing raffinate obtained in step (2), WO3And the content of Mo is: WO30.78g/L and 7.23g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO38.76g/L and 2.05g/L of Mo.
Example 2
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.8, and the pH was adjusted to 7.0 with sulfuric acid, wherein WO was contained in the tungsten-molybdenum mixed solution3And the concentration of Mo is: WO310g/L and 20g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the ether amide ionic liquid [ P66614] [ DODDGA ] is 0.2mol/L, and the volume percentage content of isooctyl alcohol is 10%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 2:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.8mol/L ammonium bicarbonate as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:2, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.97g/L and 15.48g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO38.52g/L and 3.16g/L of Mo.
Example 3
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.4, and the pH was adjusted to 7.5 with sulfuric acid, wherein tungsten and molybdenum were mixedIn solution WO3And the concentration of Mo is: WO330g/L and 10g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the ether amide ionic liquid [ P66614] [ DODDGA ] is 0.6mol/L, and the volume percentage content of isooctyl alcohol is 15%. The diluent is No. 260 solvent oil.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) taking 1.0mol/L ammonium bicarbonate as stripping solution, performing stripping on tungsten in the tungsten-containing organic phase obtained in the step (2), wherein the ratio of the stripping solution to the organic phase is 1:1, the stripping time is 3 minutes, after the stripping, the tungsten enters the stripping solution (water phase), the stripping solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing stripping solution, the number of stripping stages is 1, and the rest organic phase can be recycled after being washed by water.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate31.42g/L and 6.98g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO325.44g/L and 1.96g/L of Mo.
Example 4
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.8, and the pH was adjusted to 6.0 with sulfuric acid, wherein WO was contained in the tungsten-molybdenum mixed solution3And the concentration of Mo is: WO32g/L and 20g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ D2EHDDGA ] is 0.1mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is n-heptane.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.6mol/L sodium hydroxide as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:1, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.04g/L and 18.69g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO31.84g/L and 0.86g/L of Mo.
Example 5
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the mixed solution of tungsten and molybdenum in this example was 9.2, and the pH was adjusted to 5.8 with sulfuric acid, wherein WO was contained in the mixed solution of tungsten and molybdenum3And the concentration of Mo is: WO35g/L of Mo and 5g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the ether amide ionic liquid [ P66614] [ D2EHDDGA ] is 0.1mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) taking 1.0mol/L sodium carbonate as stripping solution, performing stripping on tungsten in the tungsten-containing organic phase obtained in the step (2), wherein the ratio of the stripping solution to the organic phase is 1:1, the stripping time is 3 minutes, after the stripping, the tungsten enters the stripping solution (water phase), the stripping solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing stripping solution, the number of stripping stages is 1, and the rest organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.67g/L and 3.56g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO33.68g/L and Mo is 0.64 g/L.
Example 6
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the mixed solution of tungsten and molybdenum in this example was 9.8, and the pH was adjusted to 7.2 with sulfuric acid, wherein WO was contained in the mixed solution of tungsten and molybdenum3And the concentration of Mo is: WO330g/L of Mo and 30g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ DODDGA ] is 1.0mol/L, and the volume percentage content of isooctyl alcohol is 10%. The diluent is n-heptane.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) taking 1.5mol/L sodium hydroxide as stripping solution, performing stripping on tungsten in the tungsten-containing organic phase obtained in the step (2), wherein the ratio of the stripping solution to the organic phase is 2:1, the stripping time is 3 minutes, after the stripping, the tungsten enters the stripping solution (water phase), the stripping solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing stripping solution, the number of stripping stages is 1, and the rest organic phase can be recycled after being washed by water.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate33.35g/L and 22.84g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO312.14g/L and 2.69g/L of Mo.
Example 7
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.5, and the pH was adjusted to 5.8 with sulfuric acid, wherein WO was contained in the tungsten-molybdenum mixed solution3And the concentration of Mo is: WO310g/L of Mo and 10g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the ether amide ionic liquid [ P66614] [ DODDGA ] is 0.2mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is cyclohexane.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 2:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.8mol/L ammonium bicarbonate as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:2, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.87g/L and 7.5 g/L of Mo6 g/L; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO38.21g/L and 1.92g/L of Mo.
Example 8
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the mixed solution of tungsten and molybdenum in this example was 9.2, and the pH was adjusted to 7.2 with sulfuric acid, wherein WO was contained in the mixed solution of tungsten and molybdenum3And the concentration of Mo is: WO35g/L of Mo and 5g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ DODDGA ] is 0.1mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.8mol/L sodium hydroxide as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:1, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.74g/L and 3.21g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO33.84g/L and 1.12g/L of Mo.
Example 9
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the tungsten-molybdenum mixed solution of this example was 9.5, and the pH was adjusted to 5.8 with sulfuric acid, wherein WO was contained in the tungsten-molybdenum mixed solution3And the concentration of Mo is: WO310g/L of Mo and 10g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the ether amide ionic liquid [ P66614] [ D2EHDDGA ] is 0.2mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is cyclohexane.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 2:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.8mol/L ammonium bicarbonate as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:2, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.94g/L and 7.12g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO37.93g/L and 1.96g/L of Mo.
Example 10
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the mixed solution of tungsten and molybdenum in this example was 9.2, and the pH was adjusted to 7.2 with sulfuric acid, wherein WO was contained in the mixed solution of tungsten and molybdenum3And the concentration of Mo is: WO35g/L of Mo and 5g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ D2EHDDGA ] is 0.1mol/L, and the volume percentage content of isooctyl alcohol is 5%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 1:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) performing back extraction on tungsten in the tungsten-containing organic phase obtained in the step (2) by taking 0.8mol/L sodium hydroxide as a back extraction solution, wherein the ratio of the back extraction solution to the organic phase is 1:1, the back extraction time is 3 minutes, after the back extraction, the tungsten enters the back extraction solution (water phase), the back extraction solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing back extraction solution, the number of the back extraction stages is 1, and the residual organic phase can be recycled after washing.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate30.85g/L and 3.14g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO33.57g/L and 1.08g/L of Mo.
Example 11
The method for separating tungsten and molybdenum of the embodiment comprises the following steps:
(1) pretreatment of
Preprocessing tungsten-molybdenum mixed solution
The pH of the mixed solution of tungsten and molybdenum in this example was 9.8, and the pH was adjusted to 7.2 with sulfuric acid, wherein WO was contained in the mixed solution of tungsten and molybdenum3And the concentration of Mo is: WO350g/L and 40g/L of Mo.
Preparation of organic phase
Preparing an organic phase containing the etheramide ionic liquid, isooctyl alcohol and a diluent, wherein the concentration of each component in the organic phase is as follows: the concentration of the etheramide ionic liquid [ A336] [ DODDGA ] is 1.0mol/L, and the volume percentage content of isooctyl alcohol is 10%. The diluent is sulfonated kerosene.
(2) Extraction of tungsten from tungsten-molybdenum mixed solution by using organic phase
Mixing and oscillating the organic phase prepared in the step II and the tungsten-molybdenum mixed solution obtained by pretreatment in the step I for 10 minutes at room temperature according to the ratio of 2:1, wherein the extraction stage number is 1, after extraction is finished, tungsten is extracted into the organic phase, molybdenum is left in raffinate (water phase), the organic phase and the raffinate are in an obvious layered state, and the organic phase containing tungsten and the raffinate containing molybdenum are separated to obtain the organic phase containing tungsten and the raffinate containing molybdenum.
(3) Stripping tungsten from alkaline solutions
And (3) taking 1.5mol/L sodium hydroxide as stripping solution, performing stripping on tungsten in the tungsten-containing organic phase obtained in the step (2), wherein the ratio of the stripping solution to the organic phase is 2:1, the stripping time is 3 minutes, after the stripping, the tungsten enters the stripping solution (water phase), the stripping solution and the organic phase are in an obvious layered state, separating to obtain the tungsten-containing stripping solution, the number of stripping stages is 2, and the rest organic phase can be recycled after being washed by water.
(4) Determination of results
Respectively carrying out WO treatment on the molybdenum-containing raffinate obtained in the step (2) and the tungsten-containing strip liquor obtained in the step (3)3And Mo content were measured to obtain the following results: determination of WO in raffinate33.47g/L and 32.15g/L of Mo; for the stripping solution containing tungsten obtained in step (3), WO3And the content of Mo is: WO311.26g/L and 1.79g/L of Mo.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
Claims (10)
1. A method for separating tungsten and molybdenum is characterized by comprising the following steps:
extracting tungsten in a tungsten-molybdenum mixed solution with the pH of 5.5-7.5 by using an organic phase containing etheramide ionic liquid and a diluent, wherein the tungsten is extracted into the organic phase, and the molybdenum is left in a raffinate, so that the separation of the tungsten and the molybdenum is realized;
the cation in the ether amide ionic liquid is [ A336]]+Or [ P66614]]+；
The anion in the ether amide ionic liquid is [ DODDGA ]]-Or [ D ]2EHDDGA]-。
2. The method for separating tungsten and molybdenum according to claim 1, wherein WO is contained in the tungsten and molybdenum mixed solution3The concentration of (B) is 1g/L to 50 g/L.
3. The method for separating tungsten and molybdenum according to claim 1, wherein WO is added to the mixed solution of tungsten and molybdenum3The mass ratio of the Mo to the WO is 1: 20-20: 13The sum of the Mo concentration and the Mo concentration is less than 100 g/L.
4. The method for separating tungsten and molybdenum according to any one of claims 1 to 3, wherein the concentration of the etheramide ionic liquid in the organic phase is 0.05mol/L to 1 mol/L.
5. The method for separating tungsten and molybdenum according to any one of claims 1 to 3, wherein the organic phase further comprises isooctyl alcohol; the volume fraction of the isooctyl alcohol is 5-10%.
6. The method for separating tungsten and molybdenum according to any one of claims 1 to 3, wherein the diluent is sulfonated kerosene, No. 260 solvent oil, aviation kerosene, n-heptane or cyclohexane.
7. The method for separating tungsten and molybdenum according to any one of claims 1 to 3, wherein the volume ratio of the organic phase to the mixed solution of tungsten and molybdenum is 1/2 to 2/1.
8. The method for separating tungsten and molybdenum according to any one of claims 1 to 3, further comprising: and (3) performing back extraction on the tungsten extracted into the organic phase by using an alkaline solution as a back extraction solution to obtain a back extraction solution containing tungsten.
9. The method for separating tungsten and molybdenum according to claim 8, wherein the alkali in the alkaline solution is sodium hydroxide, ammonia water, ammonium bicarbonate, sodium carbonate or sodium bicarbonate, and the concentration of the alkali in the alkaline solution is 0.1 mol/L-1.5 mol/L.
10. The method for separating tungsten and molybdenum according to claim 8, wherein the volume ratio of the alkaline solution to the organic phase is 1/2-2/1.
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| US4278642A (en) * | 1979-05-14 | 1981-07-14 | Gte Products Corporation | Method for removing molybdenum from tungstate solutions by solvent extraction |
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