A preparation method for extracting hafnium metal from hafnium-containing waste

Abstract

The present invention relates to the technical field of hydrometallurgy, and provides a preparation method for extracting hafnium metal from hafnium-containing waste materials, comprising the following steps: S1, dissolving the hafnium-containing waste materials to obtain a dissolved solution; S2, adding an organic phase to the dissolved solution for extraction, and then subjecting the hafnium-containing organic phase to back-extraction and precipitation to obtain hafnium oxide; the organic phase comprises an extractant; the extractant comprises dioctadecyldimethylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 1:9 to 9:1. Through the above technical solution, the problems of low yield and purity in extracting hafnium metal from hafnium-containing waste materials in the related art are solved.

Description

Technical Field

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

[0002] In the modern industrial field, hafnium, as an important rare metal, mainly comes from obtaining it from ore resources or recycling and extracting it from industrial waste materials. Among them, the recycling and extraction of hafnium resources from industrial waste materials is one of the most effective ways to alleviate the tension between the supply and demand of hafnium resources. During the production of zirconium metal products (such as zirconium tubes, zirconium plates, etc.), a large amount of scraps and waste materials are generated from zirconium-containing metal processing waste. These waste materials usually contain hafnium. Generally, the waste materials are first subjected to pretreatment such as crushing and smelting, and then a suitable extraction process (such as precipitation method, pyrometallurgy method, etc.) is used to separate hafnium.

[0003] High-purity hafnium can ensure the stable electrical performance of chips. With the increasingly strict requirements for improving chip performance in the semiconductor field, the purity requirement for hafnium is getting higher and higher. Moreover, hafnium-containing waste materials usually need to go through complex extraction and processing processes to obtain hafnium. Improving the recovery rate of hafnium means that more hafnium products can be obtained with the same raw material input, thereby improving the utilization efficiency of resources and reducing the raw material cost per unit product. The existing methods for extracting hafnium metal from hafnium-containing waste materials have the problem of low recovery rate and purity of extracted hafnium metal, which needs to be solved. High-yield and high-purity hafnium metal is required to promote the utilization efficiency of industrial waste materials and drive the development of various application fields. Summary of the Invention

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

[0005] The technical solution of the present invention is as follows:

[0006] The present invention provides a preparation method for extracting hafnium metal from hafnium-containing waste materials, comprising the following steps:

[0007] S1. Dissolve the hafnium-containing waste materials to obtain a dissolution solution;

[0008] S2. After adding an organic phase to the dissolution solution for extraction, take the hafnium-containing organic phase for back-extraction, precipitation, and heat treatment to obtain hafnium oxide;

[0009] The organic phase includes an extractant;

[0010] The extractant includes dioctadecyldimethylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 1:9 to 9:1.

[0011] As a further technical solution, the extractant comprises dioctadecyldimethylammonium chloride and trioctylmethylammonium chloride with a mass ratio of 3:2 to 4:1.

[0012] In the present invention, when extracting hafnium metal from hafnium-containing waste, when the mass ratio of the extractant in the organic phase is dioctadecyldimethylammonium chloride and trioctylmethylammonium chloride with a mass ratio of 3:2 to 4:1, the yield and purity of extracting hafnium metal from hafnium-containing waste are further improved.

[0013] As a further technical solution, after dissolution, a filtration and slag removal treatment is also carried out.

[0014] As a further technical solution, a mixed solution is used during dissolution, and the mixed solution comprises a thiocyanic acid solution and an ammonium sulfate solution with a volume ratio of 1:2 to 3;

[0015] The concentration of the thiocyanic acid solution is 4 to 8 mol / L;

[0016] The concentration of the ammonium sulfate solution is 2 to 5 mol / L.

[0017] As a further technical solution, the organic phase further comprises a diluent; the diluent is one or both of ethyl acetate and n-octanol.

[0018] As a further technical solution, the diluent is ethyl acetate and n-octanol with a volume ratio of 1:4 to 4:1.

[0019] In the present invention, when the diluent is ethyl acetate and n-octanol with a volume ratio of 1:4 to 4:1, the yield and purity of extracting hafnium metal from hafnium-containing waste are further improved.

[0020] As a further technical solution, the stripping agent during stripping comprises at least one of a tartaric acid solution and an ammonium carbonate solution.

[0021] As a further technical solution, the concentration of the stripping agent is 2 to 6 mol / L.

[0022] As a further technical solution, the mass-volume ratio of the hafnium-containing waste to the mixed solution is 1 g:6 to 9 mL.

[0023] As a further technical solution, the mass-volume ratio of the extractant to the diluent is 1 g:10 to 15 mL.

[0024] As a further technical solution, the volume ratio of the dissolution solution to the organic phase is 2 to 3:1; the volume ratio of the stripping agent to the hafnium-containing organic phase is 2 to 4:1.

[0025] As a further technical solution, the precipitating agent added during precipitation is ammonia water;

[0026] The extraction temperature is 30-40°C and the extraction time is 30-60 minutes;

[0027] The back extraction temperature is 30-35° C., and the back extraction time is 40-50 min.

[0028] The working principle and beneficial effects of the present invention are:

[0029] In the present invention, when extracting metallic hafnium 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 in the dissolved solution, thereby significantly improving the yield and purity of metallic hafnium extracted from the hafnium-containing waste. DETAILED DESCRIPTION

[0030] 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 embodiments described 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 making any creative efforts are within the scope of protection of the present invention.

[0031] Example 1

[0032] A preparation method for extracting metallic hafnium from hafnium-containing waste comprises the following steps:

[0033] S1, fully mixing the hafnium-containing waste material and the mixed solution, filtering and removing slag to obtain a dissolved solution;

[0034] 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;

[0035] S2. adding an organic phase to the dissolving solution and extracting at 30° C. for 60 minutes, mixing the organic phase containing hafnium with a tartaric acid solution at 30° C., back-extracting for 50 minutes, adding ammonia water for precipitation, and heat-treating to obtain hafnium oxide;

[0036] The organic phase comprises an extractant and a diluent in a mass-volume ratio of 1 g:10 mL; the diluent is ethyl acetate; the extractant comprises dioctadecyldimethylammonium chloride and trioctylmethylammonium 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; and the concentration of the tartaric acid solution is 2 mol / L.

[0037] After testing, the impurity content in the prepared hafnium oxide was 16 ppm, and the yield of hafnium element was 93.01%.

[0038] Example 2

[0039] A preparation method for extracting hafnium metal from hafnium-containing waste, comprising the following steps:

[0040] S1. Thoroughly mix the hafnium-containing waste and the mixed solution, filter to remove slag, and obtain a dissolved solution;

[0041] Among them, the mass-volume ratio of the hafnium-containing waste to the mixed solution is 1 g:9 mL. The mixed solution includes a thiocyanic acid solution and an ammonium sulfate solution with a volume ratio of 1:3. The concentration of the thiocyanic acid solution is 8 mol / L, and the concentration of the ammonium sulfate solution is 5 mol / L;

[0042] S2. Add an organic phase to the dissolved solution, perform extraction at 40 °C for 30 min, then take the hafnium-containing organic phase and mix it with an ammonium carbonate solution at 35 °C, perform back-extraction for 40 min, add ammonia water for precipitation, and perform heat treatment to obtain hafnium oxide;

[0043] Among them, the organic phase includes an extractant and a diluent with 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 with a mass ratio of 8:1; the volume ratio of the dissolved solution 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;

[0044] After testing, the impurity content in the prepared hafnium oxide is 19 ppm, and the recovery rate of hafnium element is 92.49%.

[0045] Example 3

[0046] A preparation method for extracting hafnium metal from hafnium-containing waste, comprising the following steps:

[0047] S1. Thoroughly mix the hafnium-containing waste and the mixed solution, filter to remove slag, and obtain a dissolved solution;

[0048] Among them, the mass-volume ratio of the hafnium-containing waste to the mixed solution is 1 g:8 mL. The mixed solution includes a thiocyanic acid solution and an ammonium sulfate solution with a volume ratio of 1:3. The concentration of the thiocyanic acid solution is 6 mol / L, and the concentration of the ammonium sulfate solution is 3 mol / L;

[0049] S2. Add an organic phase to the dissolved solution, perform extraction at 35 °C for 50 min, then take the hafnium-containing organic phase and mix it with a tartaric acid solution at 32 °C, perform back-extraction for 45 min, add ammonia water for precipitation, and perform heat treatment to obtain hafnium oxide;

[0050] Among them, the organic phase includes an extractant and a diluent with a mass-volume ratio of 1 g: 12 mL; the diluent is ethyl acetate; the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 9:1; the volume ratio of the dissolution solution 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;

[0051] After testing, the impurity content in the prepared hafnium oxide is 15 ppm, and the recovery rate of hafnium element is 93.20%.

[0052] Example 4

[0053] The difference between this example and Example 3 is only that the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 1:9;

[0054] After testing, the impurity content in the prepared hafnium oxide is 14 ppm, and the recovery rate of hafnium element is 93.32%.

[0055] Example 5

[0056] The difference between this example and Example 3 is only that the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 6:1;

[0057] After testing, the impurity content in the prepared hafnium oxide is 15 ppm, and the recovery rate of hafnium element is 93.56%.

[0058] Example 6

[0059] The difference between this example and Example 3 is only that the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 1:1;

[0060] After testing, the impurity content in the prepared hafnium oxide is 13 ppm, and the recovery rate of hafnium element is 93.33%.

[0061] Example 7

[0062] The difference between this example and Example 3 is only that the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 4:1;

[0063] After testing, the impurity content in the prepared hafnium oxide is 10 ppm, and the recovery rate of hafnium element is 94.27%.

[0064] Example 8

[0065] The difference between this example and Example 3 is only that the extractant includes dimethyldioctadecylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 3:2;

[0066] After testing, the impurity content in the prepared hafnium oxide is 11 ppm, and the recovery rate of hafnium element is 94.50%.

[0067] Example 9

[0068] The difference between this example and Example 8 is only that the diluent is n-octanol;

[0069] After testing, the impurity content in the prepared hafnium oxide is 13 ppm, and the recovery rate of hafnium element is 94.41%.

[0070] Example 10

[0071] The difference between this example and Example 8 is only that the diluent is ethyl acetate and n-octanol with a volume ratio of 4:1;

[0072] After testing, the impurity content in the prepared hafnium oxide is 8 ppm, and the recovery rate of hafnium element is 95.58%.

[0073] Example 11

[0074] The difference between this example and Example 8 is only that the diluent is ethyl acetate and n-octanol with a volume ratio of 1:4;

[0075] After testing, the impurity content in the prepared hafnium oxide is 9 ppm, and the recovery rate of hafnium element is 95.96%.

[0076] Comparative Example 1

[0077] The difference between this comparative example and Example 3 is only that the extractant is dioctadecyl dimethyl ammonium chloride;

[0078] After testing, the impurity content in the prepared hafnium oxide is 18 ppm, and the recovery rate of hafnium element is 91.78%.

[0079] Comparative Example 2

[0080] The difference between this comparative example and Example 3 is only that the extractant is trioctyl methyl ammonium chloride;

[0081] After testing, the impurity content in the prepared hafnium oxide is 20 ppm, and the recovery rate of hafnium element is 91.85%.

[0082] The hafnium oxide obtained in the above Examples 1 to 11 and Comparative Examples 1 to 2 can be reduced by sodium to obtain metallic hafnium.

[0083] Compared with Comparative Examples 1 to 2, the hafnium oxide prepared in Examples 1 to 11 has a lower impurity content and a higher recovery rate of hafnium element. It shows that when extracting metallic hafnium from hafnium-containing waste, using an extractant of dioctadecyl dimethyl ammonium chloride and trioctyl methyl ammonium chloride with a mass ratio of 1:9 to 9:1 in the organic phase to extract the hafnium element in the dissolution solution significantly improves the recovery rate and purity of extracting metallic hafnium from hafnium-containing waste.

[0084] Compared with Examples 3 to 6, the hafnium oxide prepared in Examples 7 to 8 has lower impurity content and higher recovery rate of hafnium element, indicating that when the extractant in the organic phase is dioctadecyldimethylammonium chloride and trioctylmethylammonium chloride with a mass ratio of 3:2 to 4:1, the recovery rate and purity of extracting hafnium metal from hafnium-containing waste are further improved.

[0085] Compared with Examples 8 to 9, the hafnium oxide prepared in Examples 10 to 11 has lower impurity content and higher recovery rate of hafnium element, indicating that when the diluent is ethyl acetate and n-octanol with a volume ratio of 1:4 to 4:1, the recovery rate and purity of extracting hafnium metal from hafnium-containing waste are further improved.

[0086] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, 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 preparation method for extracting hafnium metal from hafnium-containing waste materials, characterized in that, It includes the following steps: S1. Dissolve the hafnium-containing waste to obtain a dissolution solution; S2. After adding an organic phase to the dissolution solution for extraction, take the hafnium-containing organic phase for back-extraction and precipitation to obtain hafnium oxide; The organic phase includes an extractant; The extractant includes dioctadecyldimethylammonium chloride and trimethyl octyl ammonium chloride with a mass ratio of 1:9 to 9:1; A mixed solution is used during the dissolution, and the mixed solution includes a thiocyanic acid solution and an ammonium sulfate solution with a volume ratio of 1:2 to 3; The concentration of the thiocyanic acid solution is 4 to 8 mol / L; The concentration of the ammonium sulfate solution is 2 to 5 mol / L; The back-extraction agent during the back-extraction includes at least one of a tartaric acid solution and an ammonium carbonate solution.

2. The preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, wherein, Filtering and slag removal treatment is also carried out after the dissolution.

3. A preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, characterized in that, The organic phase also includes a diluent; the diluent is one or both of ethyl acetate and n-octanol.

4. The preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, characterized in that, The concentration of the back-extraction agent is 2 to 6 mol / L.

5. The preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, wherein, The mass-volume ratio of the hafnium-containing waste to the mixed solution is 1 g:6 to 9 mL.

6. The preparation method for extracting hafnium metal from hafnium-containing waste according to claim 3, characterized in that, The mass-volume ratio of the extractant to the diluent is 1 g:10 to 15 mL.

7. A preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, characterized in that, The volume ratio of the dissolution solution to the organic phase is 2 to 3:1; the volume ratio of the back-extraction agent to the hafnium-containing organic phase is 2 to 4:

1.

8. A preparation method for extracting hafnium metal from hafnium-containing waste according to claim 1, characterized in that, A precipitating agent added during the precipitation is ammonia water; The temperature during the extraction is 30 to 40 °C, and the time is 30 to 60 min; The temperature during the back-extraction is 30 to 35 °C, and the time is 40 to 50 min.