Treatment and reuse of spodumene beneficiation wastewater

Abstract

This application provides a method for treating and reusing spodumene beneficiation wastewater, belonging to the field of mineral processing wastewater treatment. This application involves formulating a composite polymeric flocculant and adding it to the spodumene beneficiation wastewater. This effectively captures fine particles suspended in the wastewater and forms larger flocs, thus achieving efficient flocculation and sedimentation. Furthermore, the supernatant after flocculation and sedimentation is sequentially subjected to ultrasonic and oxidation treatments. The force field of ultrasound enhances the oxidation process, increasing the degradation rate of organic matter. Through this method, this application can effectively reduce the chemical oxygen demand (COD) and the content of suspended solids, calcium ions, and magnesium ions in spodumene beneficiation wastewater with a simple process, less raw materials, and a shorter time. The treated wastewater can be reused in the spodumene flotation process, achieving zero discharge and recycling of spodumene beneficiation wastewater.

Description

Technical Field

[0001] This invention relates to the field of mineral processing wastewater treatment technology, specifically to a method for treating and reusing spodumene mineral processing wastewater. Background Technology

[0002] Spodumene beneficiation wastewater is characterized by high suspended solids content, the presence of heavy metal ions, and a variety of toxic and recalcitrant substances such as residual beneficiation reagents. Direct reuse of this wastewater would have a significant impact on the beneficiation process, while direct discharge would lead to water waste and environmental pollution. Therefore, the treatment and recycling of spodumene beneficiation wastewater has become a pressing problem that spodumene beneficiation plants must address.

[0003] In the prior art, for the treatment and reuse of mineral processing wastewater generated by the flotation process of spodumene ore, patent publication number CN103979719A provides a method for recycling spodumene beneficiation tailings. By adding flocculant to spodumene beneficiation tailings, after solid-liquid separation, an adsorbent is added to the liquid, after solid-liquid separation again, acid is added to the liquid for neutralization, and finally the liquid obtained after solid-liquid separation can be reused in spodumene beneficiation production.

[0004] However, when treating spodumene flotation wastewater, the flocculants used in the above methods are difficult to achieve good flocculation effects. After flocculation, absorbents need to be added for adsorption, and then acid needs to be added for neutralization. Moreover, this method is difficult to effectively reduce the COD in spodumene beneficiation wastewater.

[0005] In view of this, it is still necessary to provide an improved method for the treatment and reuse of spodumene beneficiation wastewater, to further simplify the treatment process of spodumene beneficiation wastewater and reduce the COD in spodumene beneficiation wastewater, so as to achieve zero discharge and recycling of spodumene beneficiation wastewater. Summary of the Invention

[0006] In view of the technical problems existing in the background art, this application provides a method for treating and reusing spodumene beneficiation wastewater, aiming to achieve zero discharge and simple and efficient recycling of spodumene beneficiation wastewater.

[0007] This application provides a method for treating and reusing spodumene beneficiation wastewater, including the following steps:

[0008] S1. Formulate composite polymer flocculant;

[0009] S2. Add the composite polymer flocculant to the spodumene beneficiation wastewater to carry out flocculation and sedimentation;

[0010] S3. The supernatant after flocculation and sedimentation is subjected to ultrasonic treatment;

[0011] S4. Add an oxidant to the ultrasonically treated wastewater to carry out oxidation treatment;

[0012] S5. The wastewater after oxidation treatment is subjected to solid-liquid separation, and the separated liquid phase is reused as recycled water in the flotation process of spodumene.

[0013] In the technical solution of this application embodiment, a composite polymer flocculant is formulated to improve the flocculation and sedimentation rate and sedimentation effect. Based on this, the wastewater after flocculation and sedimentation is first subjected to ultrasonic treatment, followed by oxidation treatment. The force field of the ultrasound enhances the oxidation effect, significantly improving the degradation rate and degradation effect of organic matter. Based on the technical solution provided in this application embodiment, the chemical oxygen demand (COD) and the content of suspended solids (SS), calcium ions, and magnesium ions in spodumene beneficiation wastewater can be effectively reduced.

[0014] In some embodiments, in step S1, the composite polymeric flocculant includes a first component, a second component, and water; the first component includes sodium polyacrylate and / or polydimethyldiallyl ammonium chloride; the second component includes polydimethylaminopropyl methacrylamide and polyurethane.

[0015] In this embodiment, by specifically defining the composition of the composite polymer flocculant, the synergistic effect between the components can be utilized to more efficiently form larger flocs from the tiny particles suspended in the wastewater during the flocculation and sedimentation process, thereby achieving the purpose of rapid sedimentation and water clarification. The composite polymer flocculant provided in this embodiment is designed for spodumene beneficiation wastewater. Only a small amount of flocculant is needed for effective flocculation and sedimentation. It not only significantly accelerates the flocculation rate but also has a good flocculation effect, eliminating the need for further adsorption treatment with adsorbents and effectively simplifying the treatment process.

[0016] In some embodiments, the composite polymeric flocculant has the following mass fractions: the first component is 30%–40%, the polydimethylaminopropylmethacrylamide is 30%–40%, the polyurethane is 20%–30%, and the water is 5%–10%.

[0017] In this embodiment, by limiting the amount of each component in the composite polymer flocculant, the components can work together effectively to improve the flocculation effect with less flocculant and faster flocculation speed.

[0018] In some embodiments, in step S2, the amount of the composite polymer flocculant added is 5 to 15 mg / L.

[0019] In some embodiments, the flocculation and sedimentation time in step S2 is 20 to 40 minutes.

[0020] In the above embodiments, due to the excellent flocculation effect of the prepared composite polymer flocculant, a small amount of flocculant can complete the flocculation and sedimentation process in a short time, effectively improving the treatment efficiency of spodumene beneficiation wastewater.

[0021] In some embodiments, in step S3, the frequency of the ultrasonic treatment is 20-30 kHz and the power is 600-1000 W.

[0022] In some embodiments, the ultrasonic treatment time in step S3 is 2 to 10 minutes.

[0023] In some embodiments, in step S4, the oxidant is hydrogen peroxide.

[0024] In some embodiments, in step S4, the amount of the oxidant used is 20-30 mg / L.

[0025] In some embodiments, the oxidation treatment in step S4 lasts for 20 to 30 minutes.

[0026] In the above embodiments, by performing ultrasonic-hydrogen peroxide oxidation treatment in sequence and specifically defining the parameters of the ultrasonic and oxidation treatment processes, the degradation rate of organic matter in wastewater can be effectively improved and the COD content in wastewater can be significantly reduced.

[0027] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0029] Figure 1 This is a schematic diagram of the flotation process of spodumene in the embodiments of this application. Detailed Implementation

[0030] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0032] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly indicating the number, specific order, or primary and secondary relationship of the indicated technical features.

[0033] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0034] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0035] Existing flocculants are insufficient for achieving satisfactory flotation results in spodumene flotation wastewater. Not only are high-volume flocculants required and long flocculation times, but further adsorption treatment with adsorbents is also necessary after flocculation, followed by neutralization with formic acid. Furthermore, the final reflux water still exhibits high COD, failing to meet practical requirements. Therefore, this application provides a method for treating and reusing spodumene beneficiation wastewater. By developing a novel compounded polymeric flocculant, efficient flocculation and sedimentation of spodumene flotation wastewater can be achieved with lower dosage and shorter time. Furthermore, combining this with ultrasonic-oxidation treatment utilizes the force field of ultrasound to enhance oxidation, significantly improving the degradation rate and efficiency of organic matter.

[0036] Specifically, this application provides a method for treating and reusing spodumene beneficiation wastewater, including the following steps:

[0037] S1. Formulate composite polymer flocculant;

[0038] S2. Add the composite polymer flocculant to the spodumene beneficiation wastewater to carry out flocculation and sedimentation;

[0039] S3. The wastewater after flocculation and sedimentation is subjected to ultrasonic treatment;

[0040] S4. Add an oxidant to the ultrasonically treated wastewater to carry out oxidation treatment;

[0041] S5. The wastewater after oxidation treatment is subjected to solid-liquid separation, and the separated liquid phase is reused as recycled water in the flotation process of spodumene.

[0042] The above methods can effectively reduce the chemical oxygen demand (COD) and the content of suspended solids (SS), calcium ions, and magnesium ions in spodumene beneficiation wastewater, enabling 100% reuse of the recycled water in the spodumene flotation process (e.g., Figure 1 (As shown), and does not affect flotation indicators, achieving zero discharge and recycling of mineral processing wastewater. Furthermore, the method provided in this application does not require the addition of acid for neutralization, the overall process is simple, uses less raw materials, and has a short processing time, making it highly valuable for practical application.

[0043] Furthermore, in some embodiments, the composite polymeric flocculant comprises a first component, a second component, and water; the first component comprises sodium polyacrylate and / or polydimethyldiallyl ammonium chloride; the second component comprises polydimethylaminopropyl methacrylamide and polyurethane.

[0044] In the composite polymeric flocculant, the mass fraction of the first component is preferably 30% to 40%, and the sodium polyacrylate and polydimethyldiallyl ammonium chloride in the first component can be mixed in any proportion, more preferably in a 1:1 ratio; the mass fraction of polydimethylaminopropylmethacrylamide in the second component is preferably 30% to 40%, the mass fraction of polyurethane in the second component is preferably 20% to 30%, and the mass fraction of water is preferably 5% to 10%. The composite polymeric flocculant can be obtained by uniformly mixing the raw materials at room temperature.

[0045] In the above embodiments, by specifically defining the raw materials and their proportions of the composite polymer flocculant, the synergistic effect between the components can be fully utilized. During the flocculation and sedimentation process, the tiny particles suspended in the wastewater are more efficiently transformed into larger flocs, thereby achieving rapid sedimentation and water clarification. When the above composite polymer flocculant is applied to the flocculation of spodumene beneficiation wastewater, only a small amount of flocculant is needed for effective flocculation and sedimentation. Not only is the flocculation rate significantly accelerated, but it also exhibits good flocculation effect, eliminating the need for further adsorption treatment with an adsorbent, thus effectively simplifying the treatment process.

[0046] In practical applications, when using conventional polyacrylamide as a flocculant, its dosage needs to reach at least 100 mg / L, and sedimentation should last for at least 1 hour to allow most of the fine particles in the wastewater to settle. Further adsorption with an adsorbent is then required. However, using the composite polymeric flocculant formulated in this application, the dosage is only 5–15 mg / L, and the flocculation and sedimentation time is only 20–40 minutes. No further adsorption treatment with an adsorbent is needed. This significantly reduces the amount of flocculant used and shortens the flocculation and sedimentation time while still achieving excellent flocculation and sedimentation effects, effectively improving the treatment efficiency of spodumene beneficiation wastewater.

[0047] Furthermore, in some embodiments, in step S3, the frequency of the ultrasonic treatment is 20-30 kHz, the power is 600-1000 W, and the treatment time is 2-10 min; in step S4, the oxidant is hydrogen peroxide, the amount of which is preferably 20-30 mg / L, and the oxidation treatment time is preferably 20-30 min.

[0048] In the above embodiments, by performing ultrasonic-hydrogen peroxide oxidation treatment in sequence and specifically defining the parameters of the ultrasonic and oxidation treatment processes, the synergistic effect of ultrasonic treatment and oxidation treatment can be utilized. The force field of ultrasonic waves can be used to initially degrade some organic matter, which facilitates a more efficient subsequent oxidation process, effectively improving the degradation rate of organic matter in wastewater and significantly reducing the COD content in wastewater.

[0049] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0050] Example 1

[0051] This embodiment provides a method for treating and reusing spodumene beneficiation wastewater, including the following steps:

[0052] S1. Sodium polyacrylate, polydimethylaminopropyl methacrylamide, polyurethane, and water are mixed evenly in a mass ratio of 35%:35%:25%:5% to obtain a composite polymeric flocculant;

[0053] S2. Add the composite polymer flocculant prepared in step S1 to the spodumene beneficiation wastewater at a dosage of 10 mg / L for flocculation and sedimentation.

[0054] S3. After settling for 30 minutes, the supernatant after flocculation and settling is subjected to ultrasonic treatment (frequency 30kHz, power 800W) for 5 minutes.

[0055] S4. Add hydrogen peroxide to the ultrasonically treated wastewater at a dosage of 25 mg / L for oxidation treatment for 20 minutes.

[0056] S5. Solid-liquid separation is performed on the wastewater after oxidation treatment. The separated liquid phase is reused as recycled water in the spodumene flotation process. The finely ground raw ore is mixed with the recycled water to prepare a 30% slurry. After one roughing stage, rough concentrate and tailings are obtained. The specific flotation process flow diagram is as follows: Figure 1 As shown.

[0057] Example 2

[0058] This embodiment provides a method for treating and reusing spodumene beneficiation wastewater. Compared with Embodiment 1, the only difference is the change in the raw materials of the composite polymer flocculant. In this embodiment, the first component of the composite polymer flocculant is polydimethyldiallyl ammonium chloride, that is, sodium polyacrylate in Embodiment 1 is replaced with an equal mass of polydimethyldiallyl ammonium chloride. The remaining steps are the same as in Embodiment 1 and will not be repeated here.

[0059] Example 3

[0060] This embodiment provides a method for treating and reusing spodumene beneficiation wastewater. Compared with Embodiment 1, the only difference is the change in the raw materials of the composite polymer flocculant. In this embodiment, the first component of the composite polymer flocculant is equal mass of sodium polyacrylate and polydimethyldiallyl ammonium chloride. That is, in this embodiment, the composite polymer flocculant is composed of sodium polyacrylate, polydimethyldiallyl ammonium chloride, polydimethylaminopropyl methacrylamide, polyurethane, and water mixed in a mass ratio of 17.5%:17.5%:35%:25%:5%. The remaining steps are the same as in Embodiment 1 and will not be repeated here.

[0061] Examples 4-5 and Comparative Examples 1-3

[0062] Examples 4-5 and Comparative Examples 1-3 respectively provide a method for treating and reusing spodumene beneficiation wastewater. Compared with Example 1, the only difference is that the proportions of the raw materials in the composite polymer flocculant are changed. The remaining steps are the same as in Example 1 and will not be repeated here. The proportions of the raw materials in Examples 4-5 and Comparative Examples 1-3 are shown in Table 1.

[0063] Table 1 shows the formulation ratios (wt%) of the composite polymer flocculants prepared in Examples 4-5 and Comparative Examples 1-3.

[0064]

[0065]

[0066] Comparative Examples 4-5

[0067] Comparative Examples 4 and 5 respectively provide methods for treating and reusing spodumene beneficiation wastewater. Compared with Example 1, the only difference is the replacement of some raw materials in the composite polymer flocculant. In Comparative Example 4, sodium polyacrylate in the composite polymer flocculant of Example 1 is replaced with an equal mass of polyacrylamide; in Comparative Example 5, polydimethylaminopropylmethacrylamide in the composite polymer flocculant of Example 1 is replaced with an equal mass of polyacrylamide. The remaining steps are the same as in Example 1 and will not be repeated here.

[0068] Comparative Examples 6-7

[0069] Comparative Examples 6 and 7 respectively provide a method for treating and reusing spodumene beneficiation wastewater. Compared with Example 1, the only difference is that the treatment step of spodumene beneficiation wastewater is deleted. In Comparative Example 6, the ultrasonic treatment in step S3 of Example 1 is deleted; in Comparative Example 7, the oxidation treatment in step S4 of Example 1 is deleted. The remaining steps are the same as in Example 1 and will not be described again here.

[0070] To compare the treatment effects of different embodiments and comparative examples, the composition of the recycled water after treatment in each embodiment and comparative example and its effect on spodumene flotation were tested, and compared with clean water and untreated spodumene beneficiation wastewater. The results are shown in Tables 2 and 3.

[0071] Table 2. Composition of recycled water after treatment by different methods

[0072]

[0073]

[0074] Table 3. Reuse of recycled water after different treatment methods and flotation indicators after spodumene flotation.

[0075]

[0076]

[0077] As can be seen from Tables 2-3, using the spodumene wastewater treatment process provided in this application, the COD and SS contents in the wastewater are significantly reduced, and the concentrations of calcium and magnesium ions in the wastewater are also greatly reduced. This indicates that the composite polymer flocculant in this application can effectively consume the residual collector in the wastewater and achieve the effect of flocculation and sedimentation. Moreover, the effect is better when the components and processes work synergistically. The absence of any one component or process will not achieve the best effect. After using the spodumene beneficiation wastewater purification treatment technology of this invention, the beneficiation wastewater can be 100% reused in the beneficiation process, and the obtained beneficiation indicators are close to the indicators of clean water.

[0078] Specifically, in Example 3, the combined use of the composite flocculants from Examples 1 and 2 resulted in better treatment effects and improved spodumene beneficiation indicators after reuse. In Examples 4 and 5, the proportions of each component of the flocculant were appropriately adjusted and varied within a preset range, all of which effectively treated the spodumene beneficiation wastewater. This indicates that the proportions of each component of the flocculant can be appropriately adjusted within a specific range. By controlling the proportions of each component in the flocculant within a certain range, this invention can effectively leverage the synergistic effect of each component in the flocculant, achieving effective treatment of spodumene beneficiation wastewater. In Comparative Examples 1 to 3, the proportions of each component of the flocculant exceeded the preset range. Compared with Example 1, the wastewater treatment and reuse effects were worse, indicating that the flocculant components in this invention need to be controlled within a certain proportion range, and the dosage ratio of each component has a significant impact on the wastewater treatment effect.

[0079] Comparative Examples 4 and 5 used flocculants with other components, and the concentrations of COD, SS, calcium ions, and magnesium ions in their wastewater were significantly higher than those in Example 1. The recovery rate of spodumene rough concentrate after reuse was significantly lower than that in Example 1, indicating that the flocculant used in Example 1 has a better treatment effect on spodumene beneficiation wastewater.

[0080] The wastewater treatment processes in Comparative Examples 6 and 7 lacked ultrasonic treatment and oxidation treatment, respectively. The concentrations of COD, SS, calcium ions, and magnesium ions in their wastewater were significantly higher than those in Example 1. The recovery rate of spodumene crude concentrate after reuse was significantly lower than that in Example 1, indicating that the synergistic effect of ultrasonic treatment and oxidation treatment in Example 1 has a better treatment effect on spodumene beneficiation wastewater.

[0081] In summary, this application provides a method for treating and reusing spodumene beneficiation wastewater, belonging to the field of mineral processing wastewater treatment. This application, by formulating a composite polymeric flocculant and adding it to the spodumene beneficiation wastewater, effectively captures fine particles suspended in the wastewater and forms larger flocs, thus achieving efficient flocculation and sedimentation. Based on this, the wastewater after flocculation and sedimentation is then subjected to ultrasonic treatment and oxidation treatment sequentially. The force field of ultrasound is used to enhance the oxidation effect and increase the degradation rate of organic matter. Through the above methods, this application can effectively reduce the chemical oxygen demand (COD) and the content of suspended solids, calcium ions, and magnesium ions in spodumene beneficiation wastewater with a simple process, less raw materials, and a shorter time. The treated wastewater can be reused in the spodumene flotation process, achieving zero discharge and recycling of spodumene beneficiation wastewater.

[0082] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for treating and reusing spodumene beneficiation wastewater, characterized in that, Includes the following steps: S1. Formulate a composite polymeric flocculant; the composite polymeric flocculant comprises a first component, a second component, and water; the first component comprises sodium polyacrylate and / or polydimethyldiallyl ammonium chloride; the second component comprises polydimethylaminopropyl methacrylamide and polyurethane; S2. Add the composite polymer flocculant to the spodumene beneficiation wastewater to carry out flocculation and sedimentation; S3. The supernatant after flocculation and sedimentation is subjected to ultrasonic treatment; S4. Add an oxidant to the ultrasonically treated wastewater to carry out oxidation treatment; S5. The wastewater after oxidation treatment is subjected to solid-liquid separation, and the separated liquid phase is reused as recycled water in the flotation process of spodumene.

2. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In the composite polymer flocculant, the mass fraction of the first component is 30%~40%, the mass fraction of the polydimethylaminopropyl methacrylamide is 30%~40%, the mass fraction of the polyurethane is 20%~30%, and the mass fraction of water is 5%~10%.

3. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S2, the amount of the composite polymer flocculant added is 5~15 mg / L.

4. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S2, the flocculation and sedimentation time is 20-40 minutes.

5. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S3, the frequency of the ultrasonic treatment is 20~30kHz and the power is 600~1000W.

6. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S3, the ultrasonic treatment time is 2 to 10 minutes.

7. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S4, the oxidant is hydrogen peroxide.

8. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S4, the amount of oxidant used is 20~30 mg / L.

9. The method for treating and reusing spodumene beneficiation wastewater according to claim 1, characterized in that, In step S4, the oxidation treatment time is 20-30 minutes.

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