A kind of sulfuric acid-hydrogen peroxide-ozone combined modified antimony trioxide-based adsorbent and its preparation method and application

Abstract

The application discloses a kind of sulfuric acid-hydrogen peroxide-ozone combined modified diantimony trioxide-based adsorbent and its preparation method and application.Preparation method is: sulfuric acid, deionized water, antimony oxide powder and H2O2 are mixed according to proportion, heated and stirred to obtain polyhydroxy stibonic acid slurry, then O3 is introduced to carry out surface oxidation modification, solid-liquid separation, drying is obtained.The adsorbent of the application can efficiently remove arsenic, lead, bismuth and other impurities in antimony electrolyte by complexation, ligand exchange and synergistic precipitation under the premise of not introducing exogenous metal impurities, using surface hydroxyl and high-valence antimony oxygen active site.The average removal rate of arsenic, lead and bismuth can reach 83.96%, 99.77% and 95.14% respectively, and the purified liquid can be directly reused in electrolysis system.The material after impurity removal and adsorption can be regenerated and reused, and is suitable for deep purification of high-antimony-concentration strong-acid electrolyte.

Description

Technical Field

[0001] This application relates to the field of antimony electrolyte purification technology, and in particular to a sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent, its preparation method, and its application in antimony electrolyte purification. Background Technology

[0002] In the process of preparing high-purity antimony using electrolytic refining, impurities such as arsenic, lead, and bismuth in the anode plate, due to their electrode potential being very close to that of antimony, will enter the electrolyte in ionic form and co-deposit at the cathode, severely affecting the quality of high-purity antimony products (such as 5N and 6N). Currently, common methods for purifying electrolyte impurities include co-precipitation, extraction, and adsorption.

[0003] Coprecipitation primarily utilizes the ability to form precipitates with low solubility products with impurity ions, thereby removing the impurity ions through liquid-solid separation. However, it easily introduces other impurities during application, and the pH value of the system generally needs to be controlled to prevent the precipitate from dissolving back, which can easily lead to significant hydrolysis loss of the main metal, antimony. Although sulfide precipitation is effective for many heavy metals, it is difficult to meet the requirements for deep purification when treating trace impurities below the ppm level.

[0004] Extraction is a liquid-liquid separation technique that leverages the differences in the partitioning behavior of a target substance (antimony or impurities) between two immiscible liquid phases (usually an aqueous phase and an organic phase) to achieve selective separation and purification. Choosing a suitable extractant can achieve highly selective separation of specific ions. However, this method typically requires precise control of the balance between the aqueous phase (feed solution), organic phase, and back-extraction phase, involving numerous parameters (acidity, phase ratio, temperature, extraction stage, etc.), making process development and production control quite challenging.

[0005] In contrast, adsorption methods offer advantages such as ease of operation, controllable cost, strong selectivity designability, and no introduction of additional impurities, making them highly promising for deep solution purification. However, current adsorption research largely focuses on arsenic removal or copper electrolyte systems, with a lack of research specifically targeting antimony electrolyte environments with strong acidity and high antimony ion backgrounds. CN121446438A, entitled "An Antimony Electrolyte Impurity Removal Adsorbent and Its Preparation Method and Application," discloses an adsorbent specifically for antimony electrolyte impurity removal, prepared based on antimony oxide powder, sulfuric acid, and H2O2. Under optimal experimental conditions, the adsorbent prepared using this application achieves an average lead removal rate of 95.05% and an optimal removal rate exceeding 98% in antimony electrolytes; and an average bismuth removal rate of 89.70% and an optimal removal rate exceeding 95%. However, in practice, it was found that this adsorbent is ineffective at removing arsenic from antimony electrolytes, achieving only about 40% removal.

[0006] The efficient removal of lead, bismuth, and arsenic, the main impurity elements in antimony electrolytes, has always been a pursuit of those skilled in the art. Summary of the Invention

[0007] To address or partially address the problems existing in related technologies, this application provides a sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent, its preparation method, and its application in the purification of antimony electrolyte.

[0008] The preparation method of the sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent disclosed in this application includes the following steps: (1) Mix sulfuric acid with deionized water, then add antimony oxide powder, and finally add H2O2 as the initial solution for synthesis; The mass ratio of antimony oxide powder, sulfuric acid, and hydrogen peroxide added is 1:0.8~1.5:0.5~1.5; the liquid-to-solid ratio of the initial synthesis solution (mL:g) is 8~15, where the liquid-to-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder. (2) The initial synthetic liquid is heated to a certain temperature and reacted for a certain time under continuous stirring to obtain polyhydroxy antimony acid slurry; (3) O3 gas is introduced into the polyhydroxy antimony acid slurry for a certain period of time to carry out surface oxidation modification treatment to obtain the slurry after surface oxidation modification treatment; the obtained slurry is separated into solid and liquid, the solid part is collected and dried to obtain the antimony trioxide-based adsorbent modified by sulfuric acid-hydrogen peroxide-ozone combination.

[0009] Further, in step (2), the initial synthesis solution is heated to 15~90℃ and reacted for 0.5~4 h at a stirring speed of 200~600 r / min.

[0010] Furthermore, in step (3), the output of the O3 generator in the O3-containing gas is 10 g / h, and the introduction time is 0.5h~2h.

[0011] Furthermore, in step (3), the drying temperature is 55~110 ℃ and the drying time is 1~12 h.

[0012] This application also provides a sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent, which is prepared by the preparation method described above.

[0013] This application also provides an application of a sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent in the purification treatment of antimony electrolyte. The prepared sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent is added to the antimony electrolyte to be purified, and a deimpuration reaction is carried out under set temperature and stirring conditions to obtain a deimpurated liquid. The deimpurated liquid is then allowed to settle for a period of time under set temperature conditions or a centrifuge is used to perform solid-liquid separation to obtain the purified liquid and the adsorbed material after impurity removal. The mass of the antimony electrolyte impurity removal adsorbent added is 200 to 5000 times the total mass of lead, bismuth, and arsenic in the antimony electrolyte to be purified.

[0014] Furthermore, the temperature for the deimpurification reaction is 25~90 ℃ and the reaction time is 0.1~6 h.

[0015] Furthermore, the liquid after the impurity removal reaction is allowed to settle at a temperature of 15-30 ℃ for 3-24 h, or centrifuged at a speed of 500-4000 rpm for 5-30 min.

[0016] Furthermore, after the impurity-removed adsorbate is regenerated and de-leaded, bismuthed, and arseniced, it is returned to be reused as antimony trioxide raw material; the purified liquid is returned to the antimony electrolysis system for use as antimony electrolyte.

[0017] Mechanism description of this application: The antimony electrolyte adsorbent prepared in this application is actually antimony trioxide undergoing hydration and oxidative transformation under the action of sulfuric acid and hydrogen peroxide to form a solid adsorbent phase mainly composed of polyhydroxy antimonyic acid. This solid adsorbent phase contains numerous oxygen-containing groups such as Sb-OH and Sb-O on its surface and possesses certain surface active sites. Further introduction of ozone during the mixing and preparation process activates the surface of the solid particles through oxidation, which helps to increase the proportion of high-valence antimony oxygen structures and hydroxyl active sites on the material surface, thereby enhancing its binding capacity for arsenic-containing species.

[0018] During the purification process of antimony electrolyte, arsenic species first diffuse to the surface of the adsorbent and accumulate near the hydroxyl sites, high-valence antimony oxygen sites, and defect sites on the surface of polyhydroxy antimony acid. Subsequently, arsenic-containing species can form a large molecular complex precipitate composed of arsenic antimonyate, bismuth antimonyate, antimony arsenate, bismuth arsenate, and antimony bismuthate through surface complexation, ligand exchange, Sb-O-As bonding, and synergistic deposition with coexisting impurities such as As and Bi, while simultaneously adsorbing Pb. 2+ Cu 2+ It firmly "locks" the impurity ions in the composite precipitate, thereby achieving deep and irreversible removal of impurity ions.

[0019] The beneficial effects of this application are: The antimony electrolyte impurity removal adsorbent of this invention has a short preparation process, mild reaction conditions, and simple operation. Its main components are derived from the antimony oxide system, which is less likely to introduce exogenous metal impurities when treating high-antimony-concentration electrolytes. Simultaneously, it can achieve targeted removal of arsenic without significantly altering the bulk composition of the electrolyte, and also has a synergistic removal effect on lead, bismuth, and copper impurities. Furthermore, the purified liquid can be directly returned to the electrolysis system for reuse, and the adsorbed material can also be reused.

[0020] Experimental results show that the adsorbent prepared in this application achieves an average removal rate of 83.96% for arsenic, 99.77% for lead, and 95.14% for bismuth in the electrolyte. Compared to the average removal rates of 40.02% for arsenic, 95.05% for lead, and 89.70% for bismuth in patent CN121446438A ("An Adsorbent for Removing Impurities from Antimony Electrolyte and Its Preparation Method and Application"), this application demonstrates a significant advantage in removing arsenic while maintaining high removal rates for lead and bismuth. Attached Figure Description

[0021] The above and other objects, features and advantages of this application will become more apparent from the more detailed description of exemplary embodiments thereof in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same components in the exemplary embodiments thereof.

[0022] Figure 1 This is a schematic diagram of the preparation process of the antimony trioxide-based adsorbent modified by sulfuric acid-hydrogen peroxide-ozone in this application; Figure 2 This is a schematic diagram of the process flow for removing impurities from antimony electrolyte using the sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent prepared in this application. Figure 3 This is the XRD pattern of the antimony trioxide-based adsorbent modified by sulfuric acid-hydrogen peroxide-ozone in Example 1 of this application. Detailed Implementation

[0023] Embodiments of this application will now be described in more detail with reference to the accompanying drawings. While embodiments of this application are shown in the drawings, it should be understood that this application may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to make this application more thorough and complete, and to fully convey the scope of this application to those skilled in the art.

[0024] Example 1 The preparation method of the sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent in this embodiment is as follows, and the process flow is as follows: Figure 1 As shown: (1) After mixing sulfuric acid with deionized water, antimony trioxide is added, and finally H2O2 is added as the initial synthesis solution; wherein, the mass ratio of antimony oxide powder, sulfuric acid and hydrogen peroxide is 1:1.2:1.5; the liquid-solid ratio of the initial synthesis solution is 11 mL:g, and the liquid-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder; (2) Heat the slurry from step (1) to a temperature range of 90°C, and introduce 5 g of O3 (ozone generator output is 10 g / h, 0.5 h) into it, and react for 1 h under the condition of stirring speed of 200 r / min to obtain polyhydroxy antimony acid slurry. (3) The obtained polyhydroxyantimonic acid slurry is subjected to liquid-solid separation, and the solid mixture is collected and dried at 105°C for 2 hours to obtain the sulfuric acid-hydrogen peroxide-ozone combined modified antimony trioxide-based adsorbent (hereinafter referred to as impurity removal adsorbent).

[0025] The obtained impurity removal adsorbent was analyzed by XRD pattern as follows: Figure 3 As shown, the phase is H. 14 Sb 14 O 21 (OH) 42 .

[0026] The impurity-removing adsorbent prepared above is subjected to impurity removal with antimony electrolyte, and the process flow is as follows: Figure 2 As shown in Table 1, the chemical composition of the antimony electrolyte to be purified is as follows: Table 1 Chemical composition of antimony electrolyte to be purified Further, the specific operation for removing impurities from the antimony electrolyte is as follows: The impurity removal adsorbent prepared above is added to the antimony electrolyte to be purified in Table 1 according to the mass ratio of the impurity removal adsorbent to the impurities arsenic, lead and bismuth in the antimony electrolyte to be removed being 2000:1. The impurity removal reaction temperature is 60 ℃, the stirring speed is 300 r / min, and the reaction time is 2h to obtain the impurity removal reaction solution. The purified solution was allowed to settle at 15-30 °C for 24 h, followed by solid-liquid separation to obtain the purified solution and the adsorbed material. The composition of the purified solution is shown in Table 2. Table 2 Chemical composition of purified liquid Results: In this embodiment, after one impurity removal reaction, the removal rates of arsenic, lead, and bismuth in the antimony electrolyte to be removed reached 70%, 99.77%, and 96.61%, respectively.

[0027] Example 2 The preparation method of the sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent in this embodiment is as follows, and the process flow is as follows: Figure 1 As shown: (1) After mixing sulfuric acid with deionized water, antimony oxide powder is added, and finally H2O2 is added as the initial synthesis solution; wherein, the mass ratio of antimony oxide powder, sulfuric acid and hydrogen peroxide is 1:1.2:1.5; the liquid-solid ratio of the initial synthesis solution is 10 mL:g, and the liquid-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder; (2) Heat the slurry from step (1) to a temperature range of 80 °C, and introduce 20 g of O3 (ozone generator output is 10 g / h, 2h) into it, and react for 1 h under the condition of stirring speed of 500 r / min to obtain polyhydroxy antimony acid slurry. (3) The obtained polyhydroxyantimonic acid slurry is subjected to liquid-solid separation, and the solid mixture is collected and dried at 105°C for 2 hours to obtain the sulfuric acid-hydrogen peroxide-ozone combined modified antimony trioxide-based adsorbent (hereinafter referred to as impurity removal adsorbent).

[0028] The obtained impurity removal adsorbent was analyzed by XRD pattern as follows: Figure 3 As shown, the phase is H. 14 Sb 14 O 21 (OH) 42 .

[0029] The above-prepared adsorbent was subjected to impurity removal using an antimony electrolyte. The chemical composition of the antimony electrolyte to be removed is shown in Table 3. Table 3 Chemical composition of antimony electrolyte to be purified Further, the specific operation for removing impurities from the antimony electrolyte is as follows: The impurity removal adsorbent prepared above is added to the antimony electrolyte to be purified as shown in Table 3 according to the mass ratio of the impurity removal adsorbent to the impurities arsenic, lead and bismuth in the antimony electrolyte to be purified as 5000:1. The impurity removal reaction temperature is 90℃, the oscillation frequency is 200 rpm, and the reaction time is 1h to obtain the impurity removal reaction solution. The purified liquid was centrifuged at 4000 r / min for 30 min to separate the solid and liquid phases, yielding the purified liquid and the adsorbed material. The composition of the purified liquid is shown in Table 4. Table 4 Chemical composition of purified liquid Results: In this embodiment, after one impurity removal reaction, the removal rates of arsenic, lead and bismuth in the antimony electrolyte to be removed reached 97.45%, 99.77% and 97.15%, respectively.

[0030] Example 3 The preparation method of the antimony electrolyte impurity removal adsorbent in this embodiment is as follows, and the process flow is as follows: Figure 1 As shown: (1) After mixing sulfuric acid with deionized water, antimony trioxide is added, and finally H2O2 is added as the initial synthesis solution; wherein, the mass ratio of antimony oxide powder, sulfuric acid and hydrogen peroxide is 1:1.5:0.5; the liquid-solid ratio of the initial synthesis solution is 10 mL:g, and the liquid-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder; (2) Heat the slurry from step (1) to room temperature 25 °C, and introduce 10 g of O3 (ozone generator output is 10 g / h, 2 h) into it, and react for 1 h under the condition of stirring speed of 200 r / min to obtain polyhydroxy antimony acid slurry. (3) The obtained polyhydroxyantimonic acid slurry was subjected to liquid-solid separation, and the solid mixture was collected and dried at 80°C for 2 hours to obtain the antimony electrolyte impurity removal adsorbent. The composition table of the obtained antimony electrolyte impurity removal adsorbent is shown in Table 1; that is, the antimony electrolyte impurity removal adsorbent (i.e., polyhydroxyantimonic acid adsorbent) is obtained. The obtained polyhydroxyantimonic acid adsorbent was analyzed by XRD pattern as follows. Figure 3 As shown, the phase is H. 14 Sb 14 O 21 (OH) 42 .

[0031] The antimony electrolyte impurity removal adsorbent prepared above is used for antimony electrolyte impurity removal, and the process flow is as follows: Figure 2 As shown in Table 5, the chemical composition of the antimony electrolyte to be purified is as follows: Table 5 Chemical composition of antimony electrolyte to be purified Further, the specific operation for removing impurities from the antimony electrolyte is as follows: The antimony electrolyte impurity remover prepared above is added to the antimony electrolyte to be purified in Table 5 according to the mass ratio of the antimony electrolyte impurity remover to the impurities arsenic, lead and bismuth in the antimony electrolyte to be purified of 500:1. The impurity removal reaction temperature is 75℃, the oscillation frequency is 300 rpm, and the reaction time is 2 h to obtain the impurity removal reaction solution. The purified liquid was centrifuged at 4000 r / min for 10 min to separate the solid and liquid phases, yielding the purified liquid and the adsorbed material. The composition of the purified liquid is shown in Table 6. Table 6 Chemical composition of purified liquid Results: In this embodiment, after one impurity removal reaction, the removal rates of arsenic, lead and bismuth in the antimony electrolyte to be removed reached 75.65%, 99.77% and 90.17%, respectively.

[0032] Example 4 The preparation method of the sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent in this embodiment is as follows, and the process flow is as follows: Figure 1 As shown: (1) After mixing sulfuric acid with deionized water, antimony trioxide is added, and finally H2O2 is added as the initial synthesis solution; wherein, the mass ratio of antimony oxide powder, sulfuric acid and hydrogen peroxide is 1:1.2:1.5; the liquid-solid ratio of the initial synthesis solution is 11 mL:g, and the liquid-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder; (2) Heat the slurry from step (1) to a temperature range of 90°C, and introduce 20g of O3 (ozone generator output is 10 g / h, 2h) into it, and react for 1h under the condition of stirring speed of 200 r / min to obtain polyhydroxy antimony acid slurry. (3) The obtained polyhydroxyantimonic acid slurry is subjected to liquid-solid separation, and the solid mixture is collected and dried at 105°C for 2 hours to obtain the sulfuric acid-hydrogen peroxide-ozone combined modified antimony trioxide-based adsorbent (hereinafter referred to as impurity removal adsorbent).

[0033] The obtained impurity removal adsorbent was analyzed by XRD pattern as follows: Figure 3 As shown, the phase is H. 14 Sb 14 O 21 (OH) 42 .

[0034] The impurity-removing adsorbent prepared above is subjected to impurity removal with antimony electrolyte, and the process flow is as follows: Figure 2 As shown in Table 7, the chemical composition of the antimony electrolyte to be purified is as follows: Table 7 Chemical composition of antimony electrolyte to be purified Further, the specific operation for removing impurities from the antimony electrolyte is as follows: The impurity removal adsorbent prepared above is added to the antimony electrolyte to be purified as shown in Table 7 according to the mass ratio of the impurity removal adsorbent to the impurities arsenic, lead and bismuth in the antimony electrolyte to be purified as 2000:1. The impurity removal reaction temperature is 90℃, the oscillation frequency is 200 rpm, and the reaction time is 1h to obtain the impurity removal reaction solution. The purified liquid was centrifuged at 4000 r / min for 30 min to separate the solid and liquid phases, yielding the purified liquid and the adsorbed material. The composition of the purified liquid is shown in Table 8. Table 8 Chemical composition of purified liquid Results: In this embodiment, after one impurity removal reaction, the removal rates of arsenic, lead, and bismuth in the antimony electrolyte to be removed reached 92.75%, 99.77%, and 96.61%, respectively.

[0035] In comparison, in the publication CN121446438A, titled "An Antimony Electrolyte Impurity Removal Adsorbent and Its Preparation Method and Application", the removal rates of arsenic, lead, and bismuth in antimony electrolyte were 40.02%, 99.4%, and 95.12%, respectively, under the same addition ratio.

[0036] The various embodiments of this application have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing a sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent, characterized in that, Includes the following steps: (1) Mix sulfuric acid with deionized water, then add antimony oxide powder, and finally add H2O2 as the initial solution for synthesis; The mass ratio of antimony oxide powder, sulfuric acid, and hydrogen peroxide added is 1:0.8~1.5:0.5~1.5; the liquid-to-solid ratio of the initial synthesis solution (mL:g) is 8~15, where the liquid-to-solid ratio is the ratio of the total liquid volume to the mass of antimony oxide powder. (2) The initial synthetic liquid is heated to a certain temperature and reacted for a certain time under continuous stirring to obtain polyhydroxy antimony acid slurry; (3) O3 gas is introduced into the polyhydroxy antimony acid slurry for a certain period of time to carry out surface oxidation modification treatment to obtain the slurry after surface oxidation modification treatment; the obtained slurry is separated into solid and liquid, the solid part is collected and dried to obtain the antimony trioxide-based adsorbent modified by sulfuric acid-hydrogen peroxide-ozone combination.

2. The preparation method according to claim 1, characterized in that, In step (2), the initial synthesis solution is heated to 15~90℃ and reacted for 0.5~4 h at a stirring speed of 200~600 r / min.

3. The preparation method according to claim 1, characterized in that, In step (3), the output of the O3 generator in the O3-containing gas is 10 g / h, and the introduction time is 0.5h to 2h.

4. The preparation method according to claim 1, characterized in that, In step (3), the drying temperature is 55~110℃ and the drying time is 1~12 h.

5. A sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 4.

6. The application of sulfuric acid-hydrogen peroxide-ozone co-modified antimony trioxide-based adsorbent in the purification treatment of antimony electrolyte, characterized in that, The antimony trioxide-based adsorbent modified by sulfuric acid-hydrogen peroxide-ozone as described in claim 5 is added to the antimony electrolyte to be purified, and a deimpurity reaction is carried out under the set temperature and stirring conditions to obtain the deimpurity reaction liquid; the deimpurity reaction liquid is allowed to stand and settle for a period of time under the set temperature conditions or a centrifuge is used to perform solid-liquid separation to obtain the purified liquid and the deimpurity adsorbed material. The mass of the antimony electrolyte impurity removal adsorbent added is 200 to 5000 times the total mass of lead, bismuth, and arsenic in the antimony electrolyte to be purified.

7. The application according to claim 6, characterized in that, The temperature for the impurity removal reaction is 25~90 ℃ and the reaction time is 0.1~6 h.

8. The application according to claim 6, characterized in that, The purified liquid was allowed to settle at a temperature of 15-30 ℃ for 3-24 h, or centrifuged at a speed of 500-4000 rpm for 5-30 min.

9. The application according to claim 6, characterized in that, After the impurity-removing adsorption material is regenerated and de-leaded, bismuthed, and arseniced, it is returned to be reused as antimony trioxide raw material; the purified liquid is returned to the antimony electrolysis system for use as antimony electrolyte.

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