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Method for extracting and separating tungsten and molybdenum from molybdenum-contained ammonium tungstate solution

A technology of molybdenum tungstic acid and ammonium solution, applied in the direction of improving process efficiency, etc., can solve problems such as large amount of waste water, decline in the grade of molybdenum products, unfavorable added value of molybdenum products, etc., and achieve the effect of high separation efficiency and wide application range

Active Publication Date: 2018-07-31
CENT SOUTH UNIV
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The limitations of the above research for removing molybdenum in ammonium tungstate solution are: (1) taking the chloride salt of quaternary ammonium salt as the extractant will inevitably introduce chloride ions in the ammonium tungstate solution, and chloride ions are corrosive, resulting in subsequent When the ammonium tungstate solution is evaporated and crystallized to produce APT, the equipment material needs to improve the corrosion resistance level; (2) In order to ensure the deep removal of molybdenum in the tungstate solution, co-extraction of tungsten must exist in the loaded organic phase, and the loaded organic phase is not washed or Adopt NaCl, NaOH solution to wash (washing effect is limited) and carry out stripping after, not only cause the loss of tungsten but also make to contain higher tungsten in stripping solution, cause molybdenum product grade to decline, be unfavorable for the raising of the added value of molybdenum product; (3 ) The stripping liquid that adopts alkaline NaClO solution back extraction to obtain is the sodium molybdate solution that contains a large amount of chloride ions, further processing prepares ammonium molybdate product cost height, and waste water amount is big
In view of the above problems, the separation method of tungsten and molybdenum based on thiomolybdate extraction with quaternary ammonium salt has been difficult to achieve industrial application so far.

Method used

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  • Method for extracting and separating tungsten and molybdenum from molybdenum-contained ammonium tungstate solution

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Aqueous phase material liquid: industrial molybdenum-containing ammonium tungstate solution after thiolation treatment, in which WO 3 172.9g·L -1 , Mo 0.77g / L, total S 2- 3.0g / L, Mo / WO 3 = 0.45%, pH 9.75.

[0033] Organic phase: 10% N263+20% isooctyl alcohol+70% No. 260 solvent oil (percentage by volume), wherein N263 is the product code of domestic quaternary ammonium salt extractant, is a kind of methyl trialkylammonium chloride, wherein The number of carbon atoms in the three alkyl groups is 8-10, respectively. Before extraction, contact the organic phase with ammonium bicarbonate-ammonium carbonate mixed solution (total carbon concentration is 2.5mol / L, total nitrogen concentration is 3.5mol / L) in advance to chlorinate the methyl trialkyl in the organic phase Ammonium is converted to a mixture of bicarbonates and carbonates of methyltrialkylammonium.

[0034] Detergent: ammonium bicarbonate-ammonium carbonate mixed solution, wherein the total carbon concentrati...

Embodiment 2

[0041] Aqueous phase material liquid: industrial molybdenum-containing ammonium tungstate solution after thiolation treatment, in which WO 3 300.5g·L -1 , Mo 6.5g / L, total S 2- 13.5g / L, pH 10.2.

[0042] Organic phase: 10% methyl trioctyl ammonium chloride + 30% sec-octanol + 60% sulfonated kerosene (volume percentage). Before the extraction, the organic phase was contacted with ammonium bicarbonate-ammonium carbonate mixed solution (total C 2.5mol / L, total N 3.5mol / L) in advance so that the methyl trioctyl ammonium chloride in the organic phase was converted into formazan Mixture of bicarbonate and carbonate salts of trioctylammonium.

[0043] Detergent: ammonium bicarbonate-ammonium carbonate mixed solution, in which the total C is 1.0 mol / L, and the total N is 1.0 mol / L.

[0044] Oxidizing agent: 10% H 2 o 2 solution.

[0045] Stripping agent: ammonium bicarbonate-ammonium carbonate mixed solution, in which the total C is 3.0 mol / L, and the total N is 6.0 mol / L.

[...

Embodiment 3

[0050] Aqueous phase material liquid: molybdenum-containing ammonium tungstate solution after sulfidation treatment, in which WO 3 80.0g·L -1 , Mo 12.0g / L, total S 2- 18g / L, pH 8.5.

[0051] Organic phase: 15% methyl trioctyl ammonium chloride + 40% sec-octanol + 55% aviation kerosene (volume percentage). Before the extraction, the organic phase was contacted with ammonium bicarbonate-ammonium carbonate mixed solution (total C 2.5mol / L, total N 3.5mol / L) in advance so that the methyl trioctyl ammonium chloride in the organic phase was converted into formazan Mixture of bicarbonate and carbonate salts of trioctylammonium.

[0052] Detergent: ammonium bicarbonate-ammonium carbonate mixed solution, in which the total C is 3.5mol / L, and the total N is 7.0mol / L.

[0053] Oxidizing agent: 10% H 2 o 2 solution.

[0054] Stripping agent: ammonium bicarbonate-ammonium carbonate mixed solution, in which the total C is 3.0 mol / L, and the total N is 6.0 mol / L.

[0055] Operation: ...

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Abstract

The invention discloses a method for extracting and separating tungsten and molybdenum from a molybdenum-contained ammonium tungstate solution. The method comprises the steps that bicarbonate containing trialkyl methyl ammonium and an organic phase of a carbonate composite extractant of the bicarbonate are used for making contact with molybdenum-contained ammonium tungstate feed liquid subjected to vulcanization and an ammonium bicarbonate-ammonium carbonate mixed detergent correspondingly for performing fractional extraction, the molybdenum is made to enter the organic phase, the tungsten remains in a water phase, and a high-purity ammonium tungstate aqueous solution and an organic phase loaded with pure molybdenum are obtained; and then, the organic phase loaded with the pure molybdenumis oxidized through a hydrogen peroxide solution, reextraction is performed by adopting an ammonium bicarbonate-ammonium carbonate mixed solution, a high-purity ammonium molybdate solution is obtained, and an organic phase after reextraction can directly return back to extraction for repeated use without needing treatment. The method has the characteristics that the tungsten and molybdenum mutualseparation depth is high, no detrimental impurity is introduced, and high-purity tungsten and molybdenum product liquid can be obtained simultaneously.

Description

technical field [0001] The invention relates to the field of rare metal extraction and separation in hydrometallurgy, in particular to a method for extracting and separating tungsten and molybdenum from molybdenum-containing ammonium tungstate solution. Background technique [0002] Tungsten and molybdenum are important strategic rare metals, which are widely used in cemented carbide, alloy steel, electronics, defense aviation, petrochemical and other fields. Molybdenum is an impurity element that needs to be strictly controlled in tungsten products, and tungsten is an impurity element that needs to be strictly controlled in molybdenum products. 3 Mass ratio) is not more than 0.002%, and the national standard GB / T3460-2007 stipulates that the tungsten content in zero-grade MSA (ammonium molybdate) products (W / MoO 3 mass ratio) is not more than 0.015%. However, tungsten and molybdenum belong to group VIB in the periodic table of elements, and the two often coexist in their ...

Claims

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Application Information

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IPC IPC(8): C22B3/40C22B34/34C22B34/36
CPCC22B34/34C22B34/36C22B3/402Y02P10/20
Inventor 张贵清武新生关文娟曾理李青刚曹佐英肖连生
Owner CENT SOUTH UNIV
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