Preparation method for extracting metal hafnium from hafnium-containing waste

Abstract

The invention relates to the technical field of hydrometallurgy, and provides a preparation method for extracting metal hafnium from hafnium-containing waste, which comprises the following steps: S1, dissolving the hafnium-containing waste to obtain a dissolved solution; s2, an organic phase is added into the dissolving solution for extraction, a hafnium-containing organic phase is taken for back extraction and precipitation, and hafnium oxide is obtained; the organic phase comprises an extraction agent; the extracting agent comprises dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of (1: 9)-(9: 1). According to the technical scheme, the problems of low yield and purity of metal hafnium extracted from hafnium-containing waste materials in related technologies are solved.

Description

Technical Field

[0001] The invention relates to the technical field of hydrometallurgy, and in particular to a preparation method for extracting metallic hafnium from hafnium-containing waste materials. Background Art

[0002] In the modern industrial field, hafnium is an important rare metal, and its main sources include obtaining it from ore resources or recovering it from industrial waste. Among them, the recycling of hafnium resources recovered from industrial waste is the most effective way to alleviate the tight supply and demand of hafnium resources. Zirconium-containing metal processing waste will produce a large amount of scraps and waste in the process of producing zirconium metal products (such as zirconium tubes, zirconium plates, etc.). These wastes usually contain hafnium. Usually, the waste is first pre-treated by crushing, smelting, etc., and then the hafnium is separated by a suitable extraction process (such as precipitation method, pyrometallurgy, etc.).

[0003] High-purity hafnium can ensure the stability of the electrical performance of the chip. As the semiconductor field has increasingly stringent requirements for improving chip performance, the purity requirements for hafnium are getting higher and higher. In addition, waste containing hafnium usually requires complex extraction and processing to obtain hafnium. Improving the yield of hafnium means that more hafnium products can be obtained with the same raw material input, thereby improving resource utilization efficiency and reducing the raw material cost per unit product. The existing methods for extracting metallic hafnium from hafnium-containing waste have the problem of low yield and purity of metallic hafnium that needs to be solved. It is necessary to obtain metallic hafnium with high yield and high purity to promote the utilization efficiency of industrial waste and promote the development of various application fields. Summary of the invention

[0004] The invention provides a preparation method for extracting metallic hafnium from hafnium-containing waste materials, which solves the problem of low yield and purity of metallic hafnium extracted from hafnium-containing waste materials in the related art.

[0005] The technical solution of the present invention is as follows: The present invention provides a preparation method for extracting metallic hafnium from hafnium-containing waste, comprising the following steps: S1, dissolving the hafnium-containing waste to obtain a solution; S2, after adding an organic phase to the dissolving solution for extraction, taking the organic phase containing hafnium for back extraction, precipitation, and heat treatment to obtain hafnium oxide; The organic phase includes an extractant; The extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:9 to 9:1.

[0006] As a further technical solution, the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 3:2 to 4:1.

[0007] In the present invention, when extracting metallic hafnium from hafnium-containing waste, when the mass ratio of the extractant in the organic phase is 3:2-4:1 of dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride, the yield and purity of metallic hafnium extracted from the hafnium-containing waste are further improved.

[0008] As a further technical solution, filtering and deslagging treatment is also performed after the dissolution.

[0009] As a further technical solution, a mixed solution is used during the dissolution, wherein the mixed solution comprises a thiocyanate solution and an ammonium sulfate solution in a volume ratio of 1:2-3; The concentration of the thiocyanate solution is 4-8 mol / L; The concentration of the ammonium sulfate solution is 2-5 mol / L.

[0010] As a further technical solution, the organic phase also includes a diluent; the diluent is one or both of ethyl acetate and n-octanol.

[0011] As a further technical solution, the diluent is ethyl acetate and n-octanol in a volume ratio of 1:4 to 4:1.

[0012] In the present invention, when the diluent is ethyl acetate and n-octanol in a volume ratio of 1:4 to 4:1, the yield and purity of metal hafnium extracted from hafnium-containing waste are further improved.

[0013] As a further technical solution, the stripping agent during the stripping includes at least one of tartaric acid solution and ammonium carbonate solution.

[0014] As a further technical solution, the concentration of the stripping agent is 2-6 mol / L.

[0015] As a further technical solution, the mass volume ratio of the hafnium-containing waste and the mixed solution is 1 g:6-9 mL.

[0016] As a further technical solution, the mass volume ratio of the extractant to the diluent is 1g:10~15mL.

[0017] As a further technical solution, the volume ratio of the dissolving solution to the organic phase is 2-3:1; the volume ratio of the stripping agent to the hafnium-containing organic phase is 2-4:1.

[0018] As a further technical solution, the precipitant added during the precipitation is ammonia water; The extraction temperature is 30-40°C and the extraction time is 30-60 minutes; The back extraction temperature is 30-35°C and the time is 40-50min.

[0019] The working principle and beneficial effects of the present invention are: In the present invention, when extracting metallic hafnium from hafnium-containing waste, the organic phase extractant uses dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:9 to 9:1 to extract the hafnium element in the dissolved solution, thereby significantly improving the yield and purity of metallic hafnium extracted from the hafnium-containing waste. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1 A preparation method for extracting metallic hafnium from hafnium-containing waste comprises the following steps: S1, fully mixing the hafnium-containing waste material and the mixed solution, filtering and removing the residue, and obtaining a dissolved solution; The mass volume ratio of the hafnium-containing waste and the mixed solution is 1 g:6 mL, the mixed solution includes a thiocyanate solution and an ammonium sulfate solution in a volume ratio of 1:2, the concentration of the thiocyanate solution is 4 mol / L, and the concentration of the ammonium sulfate solution is 2 mol / L; S2, adding an organic phase to the dissolving solution and extracting at 30° C. for 60 minutes, taking the organic phase containing hafnium and mixing it with a tartaric acid solution at 30° C., performing back extraction for 50 minutes, adding ammonia water for precipitation, and heat treatment to obtain hafnium oxide; The organic phase includes an extractant and a diluent in a mass volume ratio of 1 g:10 mL; the diluent is ethyl acetate; the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:9; the volume ratio of the solvent to the organic phase is 2:1; the volume ratio of the tartaric acid solution to the hafnium-containing organic phase is 2:1; the concentration of the tartaric acid solution is 2 mol / L; After testing, the impurity content in the prepared hafnium oxide was 16 ppm, and the yield of hafnium element was 93.01%.

[0022] Example 2 A preparation method for extracting metallic hafnium from hafnium-containing waste comprises the following steps: S1, fully mixing the hafnium-containing waste material and the mixed solution, filtering and removing the residue, and obtaining a dissolved solution; The mass volume ratio of the hafnium-containing waste and the mixed solution is 1 g:9 mL, the mixed solution includes a thiocyanate solution and an ammonium sulfate solution in a volume ratio of 1:3, the concentration of the thiocyanate solution is 8 mol / L, and the concentration of the ammonium sulfate solution is 5 mol / L; S2, adding an organic phase to the dissolving solution and extracting at 40° C. for 30 minutes, taking the organic phase containing hafnium and mixing it with an ammonium carbonate solution at 35° C., performing back extraction for 40 minutes, adding ammonia water for precipitation, and heat treatment to obtain hafnium oxide; The organic phase includes an extractant and a diluent in a mass volume ratio of 1 g:15 mL; the diluent is ethyl acetate; the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 8:1; the volume ratio of the solvent to the organic phase is 3:1; the volume ratio of the ammonium carbonate solution to the hafnium-containing organic phase is 4:1; the concentration of the ammonium carbonate solution is 6 mol / L; After testing, the impurity content in the prepared hafnium oxide was 19 ppm, and the yield of hafnium element was 92.49%.

[0023] Example 3 A preparation method for extracting metallic hafnium from hafnium-containing waste comprises the following steps: S1, fully mixing the hafnium-containing waste material and the mixed solution, filtering and removing the residue, and obtaining a dissolved solution; The mass volume ratio of the hafnium-containing waste and the mixed solution is 1 g:8 mL, the mixed solution includes a thiocyanate solution and an ammonium sulfate solution in a volume ratio of 1:3, the concentration of the thiocyanate solution is 6 mol / L, and the concentration of the ammonium sulfate solution is 3 mol / L; S2, adding an organic phase to the dissolving solution and extracting at 35° C. for 50 minutes, taking the organic phase containing hafnium and mixing it with a tartaric acid solution at 32° C., performing back extraction for 45 minutes, adding ammonia water for precipitation, and heat treatment to obtain hafnium oxide; The organic phase includes an extractant and a diluent in a mass volume ratio of 1 g:12 mL; the diluent is ethyl acetate; the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 9:1; the volume ratio of the solvent to the organic phase is 2:1; the volume ratio of the tartaric acid solution to the hafnium-containing organic phase is 3:1; the concentration of the tartaric acid solution is 5 mol / L; After testing, the impurity content in the prepared hafnium oxide was 15 ppm, and the yield of hafnium element was 93.20%.

[0024] Example 4 The difference between this embodiment and embodiment 3 is that the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:9; After testing, the impurity content in the prepared hafnium oxide was 14 ppm, and the yield of hafnium element was 93.32%.

[0025] Example 5 The difference between this embodiment and embodiment 3 is that the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 6:1; After testing, the impurity content in the prepared hafnium oxide was 15 ppm, and the yield of hafnium element was 93.56%.

[0026] Example 6 The difference between this embodiment and embodiment 3 is that the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:1; After testing, the impurity content in the prepared hafnium oxide was 13 ppm, and the yield of hafnium element was 93.33%.

[0027] Example 7 The difference between this embodiment and embodiment 3 is that the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 4:1; After testing, the impurity content in the prepared hafnium oxide was 10 ppm, and the yield of hafnium element was 94.27%.

[0028] Example 8 The only difference between this embodiment and embodiment 3 is that the extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 3:2; After testing, the impurity content in the prepared hafnium oxide was 11 ppm, and the yield of hafnium element was 94.50%.

[0029] Example 9 The difference between this embodiment and embodiment 8 is that the diluent is n-octanol; After testing, the impurity content in the prepared hafnium oxide was 13 ppm, and the yield of hafnium element was 94.41%.

[0030] Example 10 The difference between this embodiment and embodiment 8 is that the diluent is ethyl acetate and n-octanol in a volume ratio of 4:1; After testing, the impurity content in the prepared hafnium oxide was 8 ppm, and the yield of hafnium element was 95.58%.

[0031] Embodiment 11 The difference between this embodiment and embodiment 8 is that the diluent is ethyl acetate and n-octanol in a volume ratio of 1:4; After testing, the impurity content in the prepared hafnium oxide was 9 ppm, and the yield of hafnium element was 95.96%.

[0032] Comparative Example 1 The difference between this comparative example and Example 3 is that the extractant is dioctadecyl dimethyl ammonium chloride; After testing, the impurity content in the prepared hafnium oxide was 18 ppm, and the yield of hafnium element was 91.78%.

[0033] Comparative Example 2 The difference between this comparative example and Example 3 is that the extractant is trioctylmethylammonium chloride; After testing, the impurity content in the prepared hafnium oxide was 20 ppm, and the yield of hafnium element was 91.85%.

[0034] The hafnium oxide obtained in the above Examples 1 to 11 and Comparative Examples 1 to 2 can be reduced with sodium to obtain metallic hafnium.

[0035] Compared with Comparative Examples 1 to 2, the hafnium oxides prepared in Examples 1 to 11 have lower impurity content and higher yield of hafnium elements, indicating that when metallic hafnium is extracted from hafnium-containing waste, the organic phase extractant uses dioctadecyldimethylammonium chloride and trioctylmethylammonium chloride in a mass ratio of 1:9 to 9:1 to extract the hafnium element from the dissolved solution, which significantly improves the yield and purity of metallic hafnium extracted from the hafnium-containing waste.

[0036] Compared with Examples 3 to 6, the hafnium oxide prepared in Examples 7 to 8 has lower impurity content and higher yield of hafnium element, indicating that when the mass ratio of the organic phase extractant is 3:2 to 4:1 of dioctadecyldimethylammonium chloride and trioctylmethylammonium chloride, the yield and purity of metallic hafnium extracted from hafnium-containing waste are further improved.

[0037] Compared with Examples 8 to 9, the hafnium oxide prepared in Examples 10 to 11 has lower impurity content and higher yield of hafnium element, indicating that when the diluent is ethyl acetate and n-octanol in a volume ratio of 1:4 to 4:1, the yield and purity of metallic hafnium extracted from hafnium-containing waste are further improved.

[0038] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for extracting metallic hafnium from hafnium-containing waste, characterized in that: The following steps are involved: S1, dissolving the hafnium-containing waste to obtain a solution; S2, after adding an organic phase to the dissolving solution for extraction, taking the hafnium-containing organic phase for back extraction and precipitation to obtain hafnium oxide; The organic phase includes an extractant; The extractant includes dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride in a mass ratio of 1:9 to 9:

1.

2. The method for extracting metallic hafnium from hafnium-containing waste according to claim 1, characterized in that: After the dissolution, filtering and deslagging treatment is also carried out.

3. The method for extracting metallic hafnium from hafnium-containing waste according to claim 1, characterized in that: The dissolving process uses a mixed solution, wherein the mixed solution includes a thiocyanate solution and an ammonium sulfate solution in a volume ratio of 1:2-3; The concentration of the thiocyanate solution is 4-8 mol / L; The concentration of the ammonium sulfate solution is 2-5 mol / L.

4. The method for extracting metallic hafnium from hafnium-containing waste according to claim 1, characterized in that: The organic phase also includes a diluent; the diluent is one or two of ethyl acetate and n-octanol.

5. The method for extracting metallic hafnium from hafnium-containing waste according to claim 1, characterized in that: During the stripping, the stripping agent comprises at least one of a tartaric acid solution and an ammonium carbonate solution.

6. The method for extracting metallic hafnium from hafnium-containing waste according to claim 5, characterized in that: The concentration of the stripping agent is 2-6 mol / L.

7. The method for extracting metallic hafnium from hafnium-containing waste according to claim 3, characterized in that: The mass volume ratio of the hafnium-containing waste material to the mixed solution is 1 g:6-9 mL.

8. The method for extracting metallic hafnium from hafnium-containing waste according to claim 4, characterized in that: The mass volume ratio of the extractant to the diluent is 1 g:10-15 mL.

9. The method for extracting metallic hafnium from hafnium-containing waste according to claim 5, characterized in that: The volume ratio of the dissolving solution to the organic phase is 2-3:1; the volume ratio of the stripping agent to the hafnium-containing organic phase is 2-4:

1.

10. The method for extracting metallic hafnium from hafnium-containing waste according to claim 1, characterized in that: The precipitant added during the precipitation is ammonia water; The extraction temperature is 30-40°C and the extraction time is 30-60 minutes; The back extraction is carried out at a temperature of 30-35° C. and for a time of 40-50 min.