Method for efficiently recovering germanium and simultaneously removing harmful impurity arsenic through ultrasonic-enhanced chlorination distillation of high-grade germanium-containing material

Abstract

The invention discloses a method for efficiently recovering germanium and simultaneously removing harmful impurity arsenic through ultrasonic-enhanced chlorination distillation of a high-grade germanium-containing material, and belongs to the technical field of hydrometallurgy and comprehensive utilization of resources. The method comprises the following steps: mixing a high-grade germanium-containing material, a hydrochloric acid solution and sodium hypochlorite, and sequentially leaching and distilling; the leaching is carried out under an ultrasonic condition. The method for efficiently recovering germanium and simultaneously removing harmful impurity arsenic through ultrasonic-enhanced chlorination distillation of the high-grade germanium-containing material is short in process time, simple to operate and free of danger. The method for chlorination distillation of germanium in the high-grade germanium-containing material has the advantages of high germanium distillation rate, selective and efficient removal of impurity arsenic, short chlorination distillation time and the like, overcomes the defects of long chlorination distillation time, indissolvable germanium compound indissolvable in hydrochloric acid and difficult removal of impurity arsenic in other processes, and has obvious economic benefits.

Description

Technical Field

[0001] The invention relates to the technical field of hydrometallurgy and comprehensive resource utilization, and in particular to a method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurity arsenic. Background Art

[0002] With the advancement of science and technology, the application scope of germanium is constantly expanding, playing a vital role in various fields such as semiconductor industry, optical fiber communication, aerospace, aviation and medical safety. Germanium materials have an irreplaceable position in modern industry. With the continuous development of high-end germanium products, the development of cutting-edge germanium products has also received more and more attention. The application of germanium metal will continue to expand, and the demand for germanium will also increase. As a rare metal, germanium is difficult to form independent deposits and usually exists in trace amounts in minerals such as zinc ore, coal, and smoke. Therefore, improving the germanium recovery rate of germanium-containing resources has become a viable strategy to meet supply challenges. In response to this situation, comprehensive research and technological innovation on the extraction and recovery process of germanium are needed to determine more effective and environmentally sustainable methods to minimize the impact on the ecology and reduce dependence on natural resources.

[0003] In the prior art, the recovery process of germanium-containing raw materials ultimately moves towards the chlorination leaching-distillation-purification-hydrolysis process. This process involves dissolving valuable metals from solid materials into metal chlorides, and then distilling GeCl based on the different boiling points of metal chlorides. 4 , thus facilitating its separation from other impurities. However, germanium-containing raw materials generally contain arsenic impurities, which will generate AsCl during the chlorination leaching process. 3 , AsCl 3 The boiling point of GeCl 4 If not treated, it will lead to AsCl 3 Impurities with GeCl 4 The germanium in high-grade germanium-containing raw materials is usually wrapped by other impurities and is not easy to dissolve and leach, resulting in a low germanium recovery rate. Therefore, the recovery of germanium through the existing chlorination leaching-distillation-purification-hydrolysis process, especially the recovery of germanium from high-grade germanium raw materials, will not only increase the consumption of hydrochloric acid, but also cause the distillate to contain more AsCl 3 , reducing GeCl 4 Removal of arsenic impurities is important for GeCl 4 The distillation and extraction of germanium, especially the distillation and extraction of germanium from high-grade germanium raw materials, is essential.

[0004] Therefore, how to provide a method for efficiently recovering germanium, especially efficiently recovering germanium from high-grade germanium raw materials, while selectively removing arsenic is a technical problem that those skilled in the art urgently need to solve. Summary of the invention

[0005] The purpose of the present invention is to provide a method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic, so as to solve the problems existing in the above-mentioned prior art.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention is a method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic, comprising the following steps:

[0008] Mixing high-grade germanium-containing materials, hydrochloric acid solution and sodium hypochlorite, and sequentially performing leaching and distillation;

[0009] The leaching is carried out under ultrasonic conditions (the overall process of leaching and distilling the high-grade germanium-containing material in a hydrochloric acid solution under ultrasonic conditions can be referred to as ultrasonic enhanced chlorination distillation);

[0010] The high-grade germanium-containing material has a germanium content of 18-32wt%, and an arsenic content of 0.8-2.6wt%.

[0011] Under the action of ultrasound, the solid particles of high-grade germanium-containing materials are broken, and the insoluble germanium compounds are exposed, which increases the efficiency of solid-liquid contact, improves the leaching rate of germanium in high-grade germanium-containing materials, and further improves its distillation rate. In addition, the added sodium hypochlorite can effectively oxidize the arsenic in the high-grade germanium-containing materials into a high-priced non-volatile compound AsCl 5 , thereby fixing the arsenic in the solution to prevent the impurity arsenic from distilling into the distillate, thereby achieving efficient removal of arsenic.

[0012] Furthermore, the composition of the high-grade germanium-containing material includes Zn 2 GeO 4 、ZnGeO 3 , Pb 2 Sb 2 O 7 and As 2 O 3 .

[0013] The main reactions involved in the leaching and distillation process of the present invention are as follows:

[0014] (1) Zn 2 GeO 4 (s)+8HCl(l)→2ZnCl 2 +GeCl 4 (l)+4H 2 O;

[0015] (2) ZnGeO 3 (s)+6HCl(l)→ZnCl 2 +GeCl 4 (l)+3H 2 O;

[0016] (3)NaClO+2HCl→NaCl+H 2 O+Cl 2 ↑;

[0017] (4)AsCl 3 +Cl 2 →AsCl 5 .

[0018] The germanium in the high-grade germanium-containing material of the present invention mainly exists in the form of germanate, and a small amount of germanium exists in the form of oxide. The arsenic in the high-grade germanium-containing material mainly exists in the form of arsenic trioxide (As 2 O 3 ) and reacts with hydrochloric acid to form AsCl 3 , AsCl 3 The boiling point of GeCl 4 If it is not treated, the arsenic impurities will be produced during the distillation process along with the germanium tetrachloride (GeCl 4 ) is evaporated together, which poses a threat to the green extraction process of germanium. Therefore, the present invention introduces sodium hypochlorite as an oxidant to oxidize it into a non-volatile high-valent arsenic compound AsCl 5 , to mitigate the adverse effects of arsenic on the distillation of germanium tetrachloride.

[0019] Under the multiple effects of ultrasound, the inclusions of the high-grade germanium-containing material in the present invention, which are wrapped by impurities such as antimony (Sb) and lead (Pb), are opened, and some of the wrapped insoluble germanium compounds are exposed, which accelerates the solid-liquid contact efficiency and improves the solubility of germanium. In addition, the ultrasonic cavitation effect causes the formation of bubbles. As the bubbles grow and rupture, the energy in the bubbles is released, generating microjets and shock waves in the solution, weakening the boundary layer of the solid-liquid reaction interface. The rupture of the solid interface generates a new reaction interface, allowing the reaction to continue. Sodium hypochlorite can effectively convert AsCl 3 Oxidized to high boiling point compound AsCl 5 , to avoid the evaporation of impurity arsenic compounds during the distillation process. In addition, sodium hypochlorite, in addition to being an oxidant, can also react with hydrochloric acid to produce sodium chloride and chlorine, changing its own concentration in the solution and the concentration of hydrochloric acid, thereby increasing the solubility of germanium tetrachloride in the solution and effectively improving the germanium leaching rate, distillation rate and arsenic removal rate.

[0020] Furthermore, the specific operation of mixing the high-grade germanium-containing material, the hydrochloric acid solution and the sodium hypochlorite is: firstly uniformly mixing the high-grade germanium-containing material and the hydrochloric acid solution, and then adding the sodium hypochlorite.

[0021] Furthermore, the concentration of the hydrochloric acid solution is 7-11 mol / L, preferably 9 mol / L.

[0022] At the above concentration of hydrochloric acid solution, it can ensure that there is enough Cl in the reaction system. - Fully react with germanium compounds, and Cl - The increase of is conducive to the formation of complexes with germanium, and more germanium enters the solution in the form of soluble compounds, while ensuring the generated GeCl 4 The solubility of the hydrochloric acid solution increases the content of germanium in the solution. The concentration of the hydrochloric acid solution is further reduced, and Cl - The reaction with the germanium compound is not sufficient, and further increase in the concentration of the hydrochloric acid solution will lead to GeCl 4 The solubility is reduced.

[0023] Furthermore, the usage ratio of the high-grade germanium-containing material to the hydrochloric acid solution is 1 g:5-10 mL, preferably 1 g:7 mL.

[0024] Furthermore, the mass ratio of the high-grade germanium-containing material to the sodium hypochlorite is 1:0.15-0.35, preferably 1:0.25.

[0025] The hydrochloric acid solution and sodium hypochlorite, when added in the above amounts, can ensure that the germanium in the high-grade germanium-containing material is fully leached and recovered by distillation, and the trivalent arsenic in the solution is efficiently converted into pentavalent arsenic, and the impurity arsenic is selectively removed without causing waste of acid and oxidant, thus saving the cost of chlorination distillation.

[0026] Furthermore, the power of the ultrasonic wave is 0-100 W / L and is not 0, preferably 70 W / L.

[0027] Under the above-mentioned ultrasonic power density, high-grade germanium-containing materials are crushed into finer particles, which promotes the contact between solid particles and hydrochloric acid, increases the leaching rate, and significantly shortens the leaching time. At the same time, it can effectively open the inclusions wrapped by impurities such as antimony and lead, so that the insoluble germanium compounds are dissolved in hydrochloric acid, achieving the effect of efficient and rapid chlorination distillation.

[0028] Furthermore, the leaching temperature is 60-70°C, preferably 70°C, and the leaching time is 20 minutes.

[0029] Furthermore, the distillation temperature is 110-120°C.

[0030] Furthermore, the leaching and distillation are carried out under stirring conditions.

[0031] Furthermore, the stirring speed is 50-250r / min.

[0032] Furthermore, after the distillation is completed, the process also includes collecting the distillate (the distillate is the germanium tetrachloride solution), and filtering and washing the remaining components (the undistilled leachate).

[0033] Furthermore, the washing specifically includes washing the filtered residue with a hydrochloric acid solution, and filtering again after the washing is completed; the concentration of the hydrochloric acid solution is 7-11 mol / L.

[0034] Furthermore, before the distillation, the process also includes placing 50-200 mL of hydrochloric acid solution in a device for collecting distillate, the purpose of which is to better absorb part of the uncondensed germanium tetrachloride gas, and the hydrochloric acid solution placed in advance serves as part of the collected distillate; the concentration of the hydrochloric acid solution is 7-11 mol / L.

[0035] The present invention discloses a method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic. Under the action of ultrasonic waves, solid particles of high-grade germanium-containing materials are broken, and the wrapped insoluble germanium compounds are exposed, which increases the efficiency of solid-liquid contact and can improve the leaching rate and distillation rate of germanium in high-grade germanium-containing materials. In addition, the added sodium hypochlorite can effectively oxidize the arsenic in the high-grade germanium-containing materials into a high-priced non-volatile compound AsCl 5 , thereby fixing arsenic in the solution to prevent the impurity arsenic from distilling into the distillate, and achieving efficient removal of arsenic; and the amount of sodium hypochlorite solid added is easy to control, which is not easy to cause waste of raw materials, and fixing arsenic in the solution avoids the subsequent impurity removal process of the distillate, reducing production costs. In addition, by optimizing various influencing parameters, the present invention achieves the goal of increasing the distillation rate of germanium while selectively fixing the harmful impurity arsenic in the solution, effectively preventing the impurity arsenic from distilling into the distillate, making the distillation rate of germanium higher than 96%, and the removal rate of arsenic higher than 94%, achieving the purpose of comprehensive utilization of resources and harmless treatment.

[0036] The present invention discloses the following technical effects:

[0037] The method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and simultaneously remove harmful impurity arsenic has short process time, simple operation and no danger. The method of the present invention is used to chlorinate and distill germanium in high-grade germanium-containing materials, which has the advantages of high germanium leaching rate, high distillation rate, selective and efficient removal of impurity arsenic and short chlorination distillation time, etc. It overcomes the shortcomings of other processes such as long chlorination distillation time, insoluble germanium compounds being insoluble in hydrochloric acid, and impurity arsenic being difficult to remove, and has obvious economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0039] Figure 1 This is a process flow chart of the ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials for efficiently recovering germanium and removing harmful impurity arsenic at the same time;

[0040] Figure 2 This is the XRD diagram of the high-grade germanium-containing material (raw material) in Example 1 of the present invention;

[0041] Figure 3 This is the XRD diagram of the residue obtained after chlorination distillation in Example 1 of the present invention. DETAILED DESCRIPTION

[0042] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0043] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0044] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0045] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0046] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0047] The present invention provides a method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic, comprising the following steps (flow chart as shown in FIG. Figure 1 shown):

[0048] First, a high-grade germanium-containing material is uniformly mixed with a hydrochloric acid solution, and then sodium hypochlorite is added, and then leaching and distillation are performed in sequence; the leaching is performed under ultrasonic conditions (the overall process of leaching and distilling the high-grade germanium-containing material in a hydrochloric acid solution under ultrasonic conditions can be referred to as ultrasonic enhanced chlorination distillation); after the distillation is completed, the distillate is collected, and the remaining components (the undistilled leachate) are filtered to obtain a filtrate 1 and a filter residue 1, and the filter residue 1 is washed with a hydrochloric acid solution (with a concentration of 7-11 mol / L), and after washing, it is filtered again to obtain a filtrate 2 and a filter residue 2, and the filter residue 2 is used as the final residue (i.e. Figure 1 The distillation residue in the distillation), filtrate 1 and filtrate 2 are combined as the final residue (i.e. Figure 1 distillation residue in

[0049] The high-grade germanium-containing material has a germanium content of 18-32wt%, and an arsenic content of 0.8-2.6wt%.

[0050] As a preferred embodiment of the present invention, the composition of the high-grade germanium-containing material includes Zn 2 GeO 4 、ZnGeO 3 , Pb 2 Sb 2 O 7 and As 2 O 3 .

[0051] As a preferred embodiment of the present invention, the concentration of the hydrochloric acid solution is 7-11 mol / L, preferably 9 mol / L.

[0052] As a preferred embodiment of the present invention, the usage ratio of the high-grade germanium-containing material to the hydrochloric acid solution is 1 g:5-10 mL, preferably 1 g:7 mL.

[0053] As a preferred embodiment of the present invention, the mass ratio of the high-grade germanium-containing material to the sodium hypochlorite is 1:0.15-0.35, preferably 1:0.25.

[0054] As a preferred embodiment of the present invention, the power density of the ultrasonic wave is 0-100 W / L and is not 0, preferably 70 W / L.

[0055] As a preferred embodiment of the present invention, the leaching temperature is 60-70°C, preferably 70°C, and the leaching time is 20 minutes.

[0056] As a preferred embodiment of the present invention, the distillation temperature is 110-120°C.

[0057] As a preferred embodiment of the present invention, the leaching and distillation are carried out under stirring conditions, and the stirring speed is 50-250r / min.

[0058] As a preferred embodiment of the present invention, before the distillation, the process further comprises placing 50-200 mL of hydrochloric acid solution in a device for collecting the distillate; the concentration of the hydrochloric acid solution is 7-11 mol / L.

[0059] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0060] The high-grade germanium-containing raw materials used in the following examples and comparative examples are mainly composed of germanium-containing compounds and arsenic-containing compounds; the germanium-containing compound is germanate (Zn 2 GeO 4 、ZnGeO 3 ) etc.; the arsenic-containing compounds are arsenic trioxide etc. The main chemical components are shown in Table 1, where the values ​​are the quantitative analysis values ​​by ICP-OES.

[0061] Table 1 Main chemical composition of high-grade germanium-containing materials

[0062] element Ge Zn As Si Sb Pb Fe Mass fraction (%) 26.20 16.02 1.73 0.96 2.62 2.20 2.41

[0063] The reagents used in the following examples and comparative examples are all common commercially available products.

[0064] In the following examples and comparative examples, Cu-Kα was used as the X-ray light source, λ=0.15416 nm, voltage ≤40 kV, current ≤40 mA, and X-ray diffractometer (XRD) (D8ADVANCE) was used for phase analysis.

[0065] Example 1

[0066] A method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium while removing harmful impurities such as arsenic, comprising the following steps:

[0067] 20 g of high-grade germanium-containing material and 140 mL of 9 mol / L hydrochloric acid solution were placed in a reaction vessel and mixed evenly (liquid-to-solid ratio was 7 mL:1 g). At the same time, 100 mL of hydrochloric acid solution (concentration was 9 mol / L) was placed in a distillate recovery bottle to better absorb part of the uncondensed germanium tetrachloride gas. The ultrasonic power density was set to 70 W / L, and sodium hypochlorite was added in an amount of 0.25 g / g (sodium hypochlorite / high-grade germanium-containing material). The leaching was carried out at 70 ° C and under the reinforcement of ultrasonic waves for 20 min to obtain a leachate. After the leaching was completed, the temperature was increased to 115 ° C and distilled for 20 min. in (no ultrasonic enhancement during the distillation process), the leaching and distillation processes were carried out under stirring conditions, and the stirring speed was 100 r / min. After the distillation was completed, the distillate was collected (the volume of the distillate was 202 mL, including the 100 mL hydrochloric acid solution placed in the distillate recovery bottle before distillation), and the remaining leaching liquid was filtered to obtain filter residue 1 and filtrate 1, the obtained filter residue 1 was washed with 50 mL of hydrochloric acid solution (concentration of 9 mol / L), and filtered again to obtain filter residue 2 and filtrate 2, and the filter residue 2 was used as the final residue (the mass after drying was 3.19 g), and the filtrate 1 and the filtrate 2 were combined as the final residual liquid.

[0068] The XRD pattern of high-grade germanium-containing materials is shown in Figure 2 The XRD pattern of the residue is shown in Figure 3 .

[0069] according to Figure 2 and Figure 3 It can be seen that the XRD spectrum of high-grade germanium-containing raw materials contains Zn 2 GeO 4 、ZnGeO 3 , Pb 2 Sb 2 O 7 and As 2 O 3 The diffraction peaks indicate that the high-grade germanium-containing raw materials contain these components. The XRD spectrum of the residue does not contain Zn, which is easily soluble in hydrochloric acid, in the XRD spectrum of the high-grade germanium-containing raw materials. 2 GeO 4 、ZnGeO 3 The diffraction peak is Pb 2 Sb 2 O 7 and KSbOGeO 4 (The raw materials contain KSbOGeO 4 The content of is too low, so its diffraction peak is Figure 2 The characteristic diffraction peaks of Zn in the raw materials are not shown in the figure. 2 GeO 4 、ZnGeO3 The leaching and distillation of germanium in germanate has a significant effect. And the XRD diffraction peak intensity angle of the residue is small, the peak shape is blunt, and the peak area is small. This indicates that the impurity content of the residue is low, which indirectly proves that ultrasonic assistance is beneficial to the removal of Zn in high-grade germanium-containing materials 2 GeO 4 、ZnGeO 3 Dissolution and leaching.

[0070] Comparative Example 1

[0071] The same as Example 1, except that sodium hypochlorite was not added, the volume of the distillate obtained in this comparative example was 209 mL, and the mass of the residue (after drying) was 4.67 g.

[0072] Comparative Example 2

[0073] The same as Example 1, except that the ultrasonic power density is 0 W / L, the volume of the distillate obtained in this comparative example is 205 mL, and the mass of the residue (after drying) is 4.54 g.

[0074] Comparative Example 3

[0075] The same as Example 1, except that the ultrasonic power density is 0 W / L, the leaching time is 40 min, the distillation time is 30 min, the volume of the distillate obtained in this comparative example is 210 mL, and the mass of the residue (after drying) is 4.37 g.

[0076] Comparative Example 4

[0077] The same as Example 1, except that sodium hypochlorite is not added, the ultrasonic power density is 0 W / L, the leaching time is 40 min, the distillation time is 30 min, the volume of the distillate obtained in this comparative example is 207 mL, and the mass of the residue (after drying) is 5.28 g.

[0078] Comparative Example 5

[0079] The same as Example 1, except that sodium hypochlorite was replaced by an equal mass of calcium hypochlorite, the volume of the distillate obtained in this comparative example was 205 mL, and the mass of the residue (after drying) was 3.97 g.

[0080] Example 2

[0081] The same as Example 1, except that 20 g of high-grade germanium-containing material and 100 mL of hydrochloric acid solution are placed in a reaction container and mixed evenly, that is, the liquid-to-solid ratio is 5 mL:1 g.

[0082] Example 3

[0083] The same as Example 1, except that 20 g of high-grade germanium-containing material and 160 mL of hydrochloric acid solution are placed in a reaction container and mixed evenly, that is, the liquid-to-solid ratio is 8 mL:1 g.

[0084] Example 4

[0085] The same as Example 1, except that 20 g of high-grade germanium-containing material and 200 mL of hydrochloric acid solution are placed in a reaction container and mixed evenly, that is, the liquid-to-solid ratio is 10 mL:1 g.

[0086] Comparative Example 6

[0087] The same as Example 1, except that 20 g of high-grade germanium-containing material and 60 mL of 9 mol / L hydrochloric acid solution are placed in a reaction container and mixed evenly, that is, the liquid-to-solid ratio is 3 mL:1 g.

[0088] Example 5

[0089] The same as Example 1, except that the concentration of the hydrochloric acid solution used is 7 mol / L.

[0090] Example 6

[0091] The same as Example 1, except that the concentration of the hydrochloric acid solution used is 11 mol / L.

[0092] Comparative Example 7

[0093] The same as Example 1, except that the concentration of the hydrochloric acid solution used is 3 mol / L.

[0094] Comparative Example 8

[0095] The same as Example 1, except that the concentration of the hydrochloric acid solution used is 5 mol / L.

[0096] Example 7

[0097] Same as Example 1, except that the added amount of the oxidant sodium hypochlorite is 0.15 g / g.

[0098] Example 8

[0099] Same as Example 1, except that the added amount of the oxidant sodium hypochlorite is 0.20 g / g.

[0100] Example 9

[0101] Same as Example 1, except that the added amount of the oxidant sodium hypochlorite is 0.30 g / g.

[0102] Example 10

[0103] Same as Example 1, except that the added amount of the oxidant sodium hypochlorite is 0.35 g / g.

[0104] Embodiment 11

[0105] A method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium while removing harmful impurities such as arsenic, comprising the following steps:

[0106] 20 g of high-grade germanium-containing material and 140 mL of 7 mol / L hydrochloric acid solution were placed in a reaction vessel and mixed evenly (liquid-to-solid ratio was 7 mL:1 g). At the same time, 100 mL of hydrochloric acid solution (concentration was 7 mol / L) was placed in a distillate recovery bottle to better absorb some of the uncondensed germanium tetrachloride gas. The ultrasonic power density was set to 50 W / L, and sodium hypochlorite was added in an amount of 0.2 g / g (sodium hypochlorite / high-grade germanium-containing material). 20 m in to obtain a leachate. After the leaching was completed, the temperature was raised to 115°C and distilled for 20 minutes (no ultrasonic enhancement was performed during the distillation process). The leaching and distillation processes were both carried out under stirring conditions at a stirring speed of 100 r / min. After the distillation was completed, the distillate was collected and the remaining leachate was filtered to obtain a filter residue 1 and a filtrate 1. The obtained filter residue 1 was washed with 50 mL of a hydrochloric acid solution (with a concentration of 7 mol / L) and filtered again to obtain a filter residue 2 and a filtrate 2. The filter residue 2 was used as the final residue, and the filtrate 1 and the filtrate 2 were combined as the final residual liquid.

[0107] Example 12

[0108] A method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium while removing harmful impurities such as arsenic, comprising the following steps:

[0109] 20 g of high-grade germanium-containing material and 140 mL of 7 mol / L hydrochloric acid solution were placed in a reaction vessel and mixed evenly (liquid-to-solid ratio was 7 mL:1 g). At the same time, 100 mL of hydrochloric acid solution (concentration was 7 mol / L) was placed in a distillate recovery bottle to better absorb some of the uncondensed germanium tetrachloride gas. The ultrasonic power density was set to 100 W / L, and sodium hypochlorite was added in an amount of 0.25 g / g (sodium hypochlorite / high-grade germanium-containing material). The mixture was leached at 70 ° C and ultrasonically enhanced for 20 min. min to obtain the leaching solution. After the leaching was completed, the temperature was raised to 115°C and distilled for 20 minutes (no ultrasonic enhancement was performed during the distillation process). The leaching and distillation processes were both carried out under stirring conditions at a stirring speed of 100 r / min. After the distillation was completed, the distillate was collected and the remaining leaching solution was filtered to obtain filter residue 1 and filtrate 1. The obtained filter residue 1 was washed with 50 mL of hydrochloric acid solution (with a concentration of 7 mol / L) and filtered again to obtain filter residue 2 and filtrate 2. The filter residue 2 was used as the final residue, and the filtrate 1 and filtrate 2 were combined as the final residual liquid.

[0110] Example 13

[0111] A method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium while removing harmful impurities such as arsenic, comprising the following steps:

[0112] 20 g of high-grade germanium-containing material and 140 mL of 9 mol / L hydrochloric acid solution were placed in a reaction vessel and mixed evenly (liquid-to-solid ratio was 7 mL:1 g). At the same time, 100 mL of hydrochloric acid solution (concentration was 9 mol / L) was placed in a distillate recovery bottle to better absorb some of the uncondensed germanium tetrachloride gas. The ultrasonic power density was set to 70 W / L, and sodium hypochlorite was added in an amount of 0.25 g / g (sodium hypochlorite / high-grade germanium-containing material). 20 m in to obtain a leachate. After the leaching was completed, the temperature was raised to 115°C and distilled for 20 minutes (no ultrasonic enhancement was performed during the distillation process). The leaching and distillation processes were both carried out under stirring conditions at a stirring speed of 100 r / min. After the distillation was completed, the distillate was collected and the remaining leachate was filtered to obtain a filter residue 1 and a filtrate 1. The obtained filter residue 1 was washed with 50 mL of a hydrochloric acid solution (with a concentration of 9 mol / L) and filtered again to obtain a filter residue 2 and a filtrate 2. The filter residue 2 was used as the final residue, and the filtrate 1 and the filtrate 2 were combined as the final residual liquid.

[0113] Test Example 1

[0114] The germanium content in the distillate and the volume of the distillate of Example 1 and Comparative Examples 1-5, the germanium and arsenic contents in the residue and the mass of the residue, the arsenic content in the residual liquid and the volume of the residual liquid were measured, and the germanium leaching rate, distillation rate and arsenic removal rate were calculated. Among them, ICP-OES quantitative analysis showed that the germanium content in the high-grade germanium-containing material was 26.2wt%, that is, 20g of the high-grade germanium-containing material contained 5.24g of germanium, and the arsenic content was 1.73wt%.

[0115] The calculation formulas involved are shown in equations (1)-(3):

[0116]

[0117] Where, X is the leaching rate of germanium; Y is the distillation rate of germanium; Z is the removal rate of arsenic; M 0 W is the mass of high-grade germanium-containing raw materials, in g; 0 M is the content of germanium in high-grade germanium-containing raw materials, %; 1 is the mass of the residue after drying, in g; W 1 is the germanium content in the residue, %; W 2 is the arsenic content in the residue, %; W 3 U is the arsenic content in high-grade germanium-containing raw materials, %; 0 is the germanium content in the distillate, in g / L; V0 is the volume of the distillate, in mL; U 1 is the arsenic content in the residual solution, in g / L; V 1 is the volume of the residual liquid, in mL.

[0118] The calculation results are shown in Table 2:

[0119] Table 2

[0120]

[0121] It can be seen from Table 2 that when sodium hypochlorite oxidant is not used or ultrasonic external field enhancement is not used (Comparative Example 1 and Comparative Example 2), the leaching rate and distillation rate of germanium are reduced, the removal rate of arsenic is reduced, and it can be seen that sodium hypochlorite oxidant has a more obvious effect on the removal of arsenic.

[0122] Moreover, under the conditions of not adding sodium hypochlorite and not using ultrasonic external field enhancement (Comparative Example 4), or only not using ultrasonic external field enhancement (Comparative Example 3), even if the leaching time and distillation time are extended, the effect of Example 1 cannot be achieved, which proves that the method of the present invention not only shortens the operation time, but also improves the leaching and distillation effect. At the same time, when other hypochlorites (such as calcium hypochlorite) are used instead of sodium hypochlorite, the effect as good as that of Example 1 cannot be achieved, which proves the advantage of using sodium hypochlorite as an oxidant, and sodium hypochlorite is cheaper and easier to obtain, and using sodium hypochlorite as an oxidant is more cost-effective.

[0123] Test Example 2

[0124] The content of germanium in the distillate and the volume of the distillate of Examples 1-4 and Comparative Example 6, the content of germanium and arsenic in the residue and the mass of the residue, the content of arsenic in the residual liquid and the volume of the residual liquid were measured, and the leaching rate of germanium, the distillation rate, and the removal rate of arsenic were calculated (the calculation method was the same as that of Example 1). The results are shown in Table 3.

[0125] Table 3

[0126]

[0127] It can be seen from Table 3 that the liquid-solid ratio has an important influence on the leaching rate of germanium during the leaching process. A good leaching rate can be achieved when the liquid-solid ratio is in the range of 5-10 mL / g, and the leaching rate has a certain trend with the change of the liquid-solid ratio. When the liquid-solid ratio is 7 mL / g, the germanium leaching rate, distillation rate, and arsenic removal rate are the highest. When the liquid-solid ratio is lower than 7 mL / g, the distillation rate of germanium and the removal rate of arsenic are lower, especially when it is lower than 5 mL / g, the distillation rate of germanium and the removal rate of arsenic are significantly reduced. The main reason is that the amount of hydrochloric acid added is small, and the H in the system is +Insufficient ions make the reaction unable to proceed completely. In addition, the larger the liquid-to-solid ratio, the lower the viscosity. When the liquid-to-solid ratio is lower than 5mL / g, the viscosity of the reaction system is relatively large, and the diffusion resistance between the solid and the liquid increases, which makes the reaction interface between the metal compound and the hydrochloric acid update slowly. When the liquid-to-solid ratio is higher than 7mL / g, the leaching rate of germanium has almost no change, and the distillation rate of germanium and the removal rate of arsenic have not changed significantly. Therefore, in order to save raw materials, it is most appropriate to take a liquid-to-solid ratio of 7mL / g.

[0128] Test Example 3

[0129] The content of germanium in the distillate and the volume of the distillate of Example 1, Examples 5-6 and Comparative Examples 7-8, the content of germanium and arsenic in the filter residue and the mass of the filter residue, the content and volume of arsenic in the residual liquid were determined, and the leaching rate of germanium, the distillation rate, and the removal rate of arsenic were calculated (the calculation method was the same as that of Test Example 1). The results are shown in Table 4.

[0130] Table 4

[0131]

[0132] As can be seen from Table 4, in the chlorination distillation process, the influence of hydrochloric acid concentration on the germanium leaching rate, distillation rate and arsenic removal rate is very significant. The hydrochloric acid concentration can achieve good germanium leaching rate, distillation rate and arsenic removal rate in the range of 7-11mol / L, and the germanium leaching rate, distillation rate and arsenic removal rate have a certain trend of change with the change of hydrochloric acid concentration. As the hydrochloric acid concentration is higher, the germanium leaching rate, distillation rate and arsenic removal rate continue to increase. When the hydrochloric acid concentration is 9mol / L, it reaches the maximum value (Example 1). This trend can be attributed to GeCl 4 Solubility behavior in hydrochloric acid. Specifically, GeCl 4 The solubility of GeCl increases first and then decreases with the increase of hydrochloric acid concentration. At the same time, the increase of chloride ion concentration makes the reaction between germanium compound and hydrochloric acid more complete. When the hydrochloric acid concentration is greater than 9 mol / L, although the reaction between germanium compound and hydrochloric acid is more complete, GeCl 4 The solubility of germanium continues to decrease, resulting in a decrease in the leaching rate and distillation rate of germanium. Therefore, the most appropriate concentration of hydrochloric acid is 9 mol / L.

[0133] Test Example 5

[0134] The content of germanium in the distillate and the volume of the distillate of Example 1 and Examples 7-10, the content of germanium and arsenic in the filter residue and the mass of the filter residue, the content and volume of arsenic in the residual liquid were determined, and the leaching rate of germanium, the distillation rate, and the removal rate of arsenic were calculated (the calculation method was the same as that of Test Example 1). The results are shown in Table 5.

[0135] Table 5

[0136]

[0137] As shown in Table 5, the amount of sodium hypochlorite added has a certain effect on the distillation rate of germanium and the removal rate of arsenic. When the amount of sodium hypochlorite added is in the range of 0.15-0.35g / g, a better distillation rate of germanium and arsenic removal rate can be achieved. The distillation rate of germanium and arsenic removal rate have a certain change trend with the addition of sodium hypochlorite. With the increase of the addition of sodium hypochlorite, the distillation of germanium first shows an upward trend, and after 0.25g / g, it shows a downward trend, and the removal rate of arsenic shows a continuous upward trend. This is because, in the hydrochloric acid solution, the addition of NaClO oxidant not only produces Cl 2 and HClO can be used as oxidants, and NaCl, H 2 O and HCl, thus affecting GeCl 4 In addition, the addition of sodium hypochlorite oxidizes trivalent arsenic to pentavalent arsenic with a high boiling point, enhancing the removal of arsenic.

[0138] Test Example 6

[0139] The content of germanium in the distillate and the volume of the distillate of Example 1 and Examples 11-13, the content of germanium and arsenic in the filter residue and the mass of the filter residue, the content and volume of arsenic in the residual liquid were determined, and the leaching rate of germanium, the distillation rate, and the removal rate of arsenic were calculated (the calculation method was the same as that of Test Example 1). The results are shown in Table 6.

[0140] Table 6

[0141]

[0142] It can be seen from Table 6 that compared with Example 1, Example 11 has lower hydrochloric acid concentration, lower leaching temperature, lower oxidant concentration and lower ultrasonic power density, so the distillation effect of Example 11 is far inferior to that of Example 1;

[0143] Compared with Example 1, Example 12 has a lower hydrochloric acid concentration, but a higher power density of ultrasonic waves. The distillation effect of Example 12 is also inferior to that of Example 1, indicating that in the chlorination distillation process, the hydrochloric acid concentration plays a decisive role in the leaching and distillation of germanium, and the effect of ultrasonic waves is less than that of hydrochloric acid.

[0144] Compared with Example 1, Example 13 has a lower leaching temperature. The low temperature reduces the movement rate of various substances in the reaction system, slows down the mass transfer rate, and reduces the probability of collision between molecules, resulting in a decrease in the reaction rate. Therefore, the distillation effect of Example 13 is not as good as that of Example 1.

[0145] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic, characterized in that: The following steps are involved: Mixing high-grade germanium-containing materials, hydrochloric acid solution and sodium hypochlorite, and sequentially performing leaching and distillation; The leaching is carried out under ultrasonic conditions; The high-grade germanium-containing material has a germanium content of 18-32wt%, and an arsenic content of 0.8-2.6wt%.

2. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The components of the high-grade germanium-containing material include Zn2GeO4, ZnGeO3, Pb2Sb2O7 and As2O3.

3. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The concentration of the hydrochloric acid solution is 7-11 mol / L.

4. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 3, characterized in that: The usage ratio of the high-grade germanium-containing material to the hydrochloric acid solution is 1g:5-10mL.

5. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The mass ratio of the high-grade germanium-containing material to the sodium hypochlorite is 1:0.15-0.

35.

6. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The power density of the ultrasonic wave is 0-100 W / L, and is not 0.

7. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The leaching temperature is 60-70°C and the leaching time is 20 minutes.

8. The method for ultrasonically enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The distillation temperature is 110-120°C.

9. The method for ultrasonic enhanced chlorination distillation of high-grade germanium-containing materials to efficiently recover germanium and remove harmful impurities such as arsenic as claimed in claim 1, characterized in that: The leaching and distillation are carried out under stirring conditions.

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