Method for treating and recycling spodumene beneficiation wastewater

Abstract

The invention provides a method for treating and recycling spodumene beneficiation wastewater, and belongs to the field of beneficiation wastewater treatment. According to the method, the composite polymeric flocculant is prepared and added into the spodumene beneficiation wastewater, fine particles suspended in the wastewater can be effectively captured, floccules with larger volumes can be formed, and therefore efficient flocculating settling is conducted; and on the basis, the supernate subjected to flocculating settling is sequentially subjected to ultrasonic treatment and oxidation treatment, so that the oxidation effect can be enhanced by utilizing a force field of ultrasonic waves, and the degradation rate of organic matters is increased. By means of the mode, the chemical oxygen demand of the spodumene beneficiation wastewater and the content of suspended solids, calcium ions and magnesium ions in the wastewater can be effectively reduced through the simple technology, few raw materials and short time, and backwater obtained after treatment can be reused in the flotation technology of spodumene; and cyclic utilization and zero emission of spodumene beneficiation wastewater are realized.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing wastewater treatment, and in particular to a method for treating and reusing spodumene mineral processing wastewater. Background Art

[0002] Spodumene beneficiation wastewater has the characteristics of high suspended matter content, heavy metal ions, beneficiation residual agents and many other toxic and difficult-to-degrade substances. If it is directly reused, it will have a huge impact on the beneficiation process, but directly discharging it will cause water resource waste and environmental pollution. Therefore, the treatment and recycling of spodumene beneficiation wastewater has become a difficult problem that spodumene beneficiation plants must face and urgently need to solve.

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

[0004] However, when the above method is used to treat spodumene flotation wastewater, the flocculant used is difficult to achieve a good flocculation effect. After flocculation, an absorbent needs to be added for adsorption, and then acid needs to be added for neutralization. In addition, 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 treating and reusing spodumene ore dressing wastewater, further simplify the treatment process of spodumene ore dressing wastewater, and reduce the COD in spodumene ore dressing wastewater, so as to achieve zero discharge and recycling of spodumene ore dressing wastewater. Summary of the invention

[0006] In view of the technical problems existing in the background technology, the present application provides a method for treating and reusing spodumene ore dressing wastewater, aiming to simply and efficiently achieve zero-discharge recycling of spodumene ore dressing wastewater.

[0007] The present application embodiment provides a method for treating and reusing spodumene beneficiation wastewater, comprising the following steps:

[0008] S1. Prepare composite polymer flocculant;

[0009] S2. Adding the composite polymer flocculant to the spodumene beneficiation wastewater for flocculation and sedimentation;

[0010] S3. Ultrasonic treatment of the supernatant after flocculation and sedimentation;

[0011] S4. adding an oxidant to the wastewater after ultrasonic treatment for oxidation treatment;

[0012] S5. performing solid-liquid separation on the wastewater after the oxidation treatment, and recycling the separated liquid phase as return water to the flotation process of spodumene.

[0013] In the technical scheme of the embodiment of the present application, the rate and sedimentation effect of flocculation and sedimentation are improved by preparing a composite polymer flocculant; on this basis, by first ultrasonically treating the wastewater after flocculation and sedimentation, and then performing oxidation treatment, the force field effect of the ultrasonic wave can strengthen the oxidation effect, so that the degradation rate and degradation effect of organic matter are greatly improved. Based on the technical scheme provided by the embodiment of the present application, the chemical oxygen demand (COD) of spodumene beneficiation wastewater and the content of suspended solids (SS), calcium ions, and magnesium ions in the wastewater can be effectively reduced.

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

[0015] In this embodiment, by specifically limiting 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 precipitation and clarification of water quality. The composite polymer flocculant provided in the embodiment of the present application is designed for spodumene beneficiation wastewater, and only a small amount of flocculant is needed to effectively carry out flocculation and sedimentation, which not only significantly accelerates the flocculation rate, but also has a good flocculation effect, and no further adsorption treatment with an adsorbent is required in the subsequent process, which effectively simplifies the treatment process.

[0016] In some embodiments, in the composite polymer flocculant, the mass fraction of the first component is 30% to 40%, the mass fraction of the polydimethylaminopropyl methacrylamide is 30% to 40%, the mass fraction of the polyurethane is 20% to 30%, and the mass fraction of water is 5% to 10%.

[0017] In this embodiment, by limiting the dosage of each component in the composite polymer flocculant, the components can be effectively coordinated to improve the flocculation effect with less flocculant dosage 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, in step S2, the flocculation and sedimentation time is 20 to 40 minutes.

[0020] In the above embodiment, 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 relatively short time, thereby 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 600-1000W.

[0022] In some embodiments, in step S3, the ultrasonic treatment time 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, in step S4, the oxidation treatment time is 20 to 30 minutes.

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

[0027] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 This is a schematic diagram of the flotation process flow of spodumene in the embodiments of the present application. DETAILED DESCRIPTION

[0030] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

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

[0033] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0034] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0035] Since the existing flocculants are difficult to achieve a good flotation effect on spodumene flotation wastewater, not only the dosage of flocculants is high and the flocculation time is long, but also an adsorbent needs to be further used for adsorption treatment after flocculation, and then formic acid needs to be neutralized, and the COD in the final return water is still high, which is difficult to meet actual needs. Based on this, the present application provides a method for treating and reusing spodumene ore dressing wastewater, by developing a new type of composite polymer flocculant, efficient flocculation and sedimentation of spodumene flotation wastewater can be achieved with a lower dosage and a shorter time, on this basis, combined with ultrasound-oxidation treatment, the force field effect of ultrasound can be used to enhance oxidation, so that the degradation rate and degradation effect of organic matter are greatly improved.

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

[0037] S1. Prepare composite polymer flocculant;

[0038] S2. Adding the composite polymer flocculant to the spodumene beneficiation wastewater for flocculation and sedimentation;

[0039] S3. Ultrasonic treatment of the wastewater after flocculation and sedimentation;

[0040] S4. adding an oxidant to the wastewater after ultrasonic treatment for oxidation treatment;

[0041] S5. performing solid-liquid separation on the wastewater after the oxidation treatment, and recycling the separated liquid phase as return water to the flotation process of spodumene.

[0042] Through the above method, the chemical oxygen demand (COD) of spodumene beneficiation wastewater and the content of suspended solids (SS), calcium ions and magnesium ions in the wastewater can be effectively reduced, so that the return water can be 100% reused in the flotation process of spodumene (such as Figure 1 As shown), and does not affect the flotation index, and realizes the recycling and zero discharge of mineral processing wastewater. In addition, the method provided by the present application does not require the addition of acid for neutralization treatment, the overall process is simple, the amount of raw materials used is small, the processing time is short, and it has high practical application value.

[0043] Furthermore, in some embodiments, the composite polymer flocculant includes a first component, a second component and water; the first component includes sodium polyacrylate and / or polydimethyldiallylammonium chloride; and the second component includes polydimethylaminopropylmethacrylamide and polyurethane.

[0044] In the composite polymer flocculant, the mass fraction of the first component is preferably 30% to 40%, the sodium polyacrylate and polydimethyldiallyl ammonium chloride in the first component can be mixed in any proportion, preferably 1:1; the mass fraction of polydimethylaminopropyl methacrylamide 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 polymer flocculant can be obtained by uniformly mixing the raw materials at room temperature.

[0045] In the above embodiment, by specifically limiting the raw materials and proportions of the composite polymer flocculant, the synergistic effect between the components can be fully utilized, and the tiny particles suspended in the wastewater can be more efficiently formed into larger flocs during the flocculation and sedimentation process, thereby achieving the purpose of rapid precipitation and clarification of water quality. When the above composite polymer flocculant is applied to the flocculation of spodumene beneficiation wastewater, only a small amount of flocculant is needed to effectively carry out flocculation and sedimentation, which not only significantly accelerates the flocculation rate, but also has a good flocculation effect, and no further adsorption treatment with an adsorbent is required in the subsequent process, which effectively simplifies the treatment process.

[0046] In practical applications, when conventional polyacrylamide is used as a flocculant, its dosage needs to be at least 100 mg / L, and the sedimentation time needs to be at least 1 hour to allow most of the fine particles in the wastewater to settle, and then an adsorbent needs to be further used for adsorption. However, when the composite polymer flocculant prepared in the embodiment of the present application is used, the addition amount of the composite polymer flocculant only needs to be 5-15 mg / L, and the flocculation and sedimentation time only needs to be 20-40 minutes. No additional adsorbent is required for adsorption treatment in the future. While greatly reducing the dosage of the flocculant and shortening the flocculation and sedimentation time, an excellent flocculation and sedimentation effect can still be achieved, effectively improving the treatment efficiency of spodumene ore dressing 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, and its dosage is preferably 20-30 mg / L, and the oxidation treatment time is preferably 20-30 min.

[0048] In the above embodiment, by performing ultrasound-hydrogen peroxide oxidation treatment in sequence and specifically defining the parameters of the ultrasound and oxidation treatment processes, the synergistic effect of ultrasound treatment and oxidation treatment can be utilized, and some organic matter can be initially degraded through the force field of ultrasound, so that the subsequent oxidation process can be carried out more efficiently, effectively improving the degradation rate of organic matter in the wastewater, and greatly reducing the COD content in the wastewater.

[0049] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer 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, comprising the following steps:

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

[0053] S2. Adding the composite polymer flocculant prepared in step S1 to the spodumene ore dressing wastewater in an amount of 10 mg / L to carry out flocculation and sedimentation;

[0054] S3. After settling for 30 min, the supernatant after the flocculation settling was subjected to ultrasonic treatment (frequency of 30 kHz, power of 800 W) for 5 min;

[0055] S4. Add hydrogen peroxide in an amount of 25 mg / L to the wastewater after ultrasonic treatment for oxidation treatment for 20 min;

[0056] S5. The wastewater after oxidation treatment is separated into solid and liquid, and the separated liquid phase is reused as backwater in the flotation process of spodumene. The ground raw ore and backwater are mixed into a slurry with a concentration of 30%, and after a roughing process, a coarse concentrate and tailings are obtained. The specific flotation process flow chart is as follows: Figure 1 shown.

[0057] Example 2

[0058] This embodiment provides a method for treating and reusing spodumene beneficiation wastewater. Compared with Example 1, the only difference is that the raw material of the composite polymer flocculant is changed. In this embodiment, the first component in the composite polymer flocculant is polydimethyldiallyl ammonium chloride, that is, the sodium polyacrylate in Example 1 is replaced with polydimethyldiallyl ammonium chloride of the same mass, and the remaining steps are consistent with Example 1 and are not repeated here.

[0059] Example 3

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

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

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

[0063] Table 1 Proportions of the composite polymer flocculants prepared in Examples 4 to 5 and Comparative Examples 1 to 3 (wt%)

[0064]

[0065]

[0066] Comparative Examples 4-5

[0067] Comparative Examples 4 and 5 respectively provide a method for treating and reusing spodumene beneficiation wastewater. Compared with Example 1, the only difference is that part of the raw materials of the composite polymer flocculant are replaced. In Comparative Example 4, the sodium polyacrylate in the composite polymer flocculant of Example 1 is replaced with polyacrylamide of the same mass; in Comparative Example 5, the polydimethylaminopropyl methacrylamide in the composite polymer flocculant of Example 1 is replaced with polyacrylamide of the same mass, and the remaining steps are the same as those in Example 1, which 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, which differs from Example 1 only in that the step of treating 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, and the remaining steps are consistent with Example 1 and are not repeated here.

[0070] In order to compare the treatment effects of different embodiments and comparative examples, the components of the returned water after treatment of each embodiment and comparative example and their effects on spodumene flotation were tested, and compared with clean water and untreated spodumene beneficiation wastewater. The results are shown in Tables 2 to 3.

[0071] Table 2 Return water components after treatment by different methods

[0072]

[0073]

[0074] Table 3 Recycling of backwater after treatment by different methods and flotation indexes after spodumene flotation

[0075]

[0076]

[0077] It can be seen from Tables 2 to 3 that, using the spodumene wastewater treatment process provided by the present application, the COD and SS contents in the wastewater are significantly reduced, and the concentrations of calcium ions and magnesium ions in the wastewater are also greatly reduced, indicating that the composite polymer flocculant in the present application can effectively consume the residual collector in the wastewater and play a flocculation and sedimentation effect, and the effect is better when the components and processes work together. The lack of one of the components or processes cannot achieve the best effect; after using the spodumene mineral processing wastewater purification treatment technology of the present invention, the mineral processing wastewater can be 100% reused in the mineral processing process, and the obtained mineral processing index is close to the clean water index.

[0078] Specifically, in Example 3, the composite flocculants in Example 1 and Example 2 are used in combination, and the treatment effect is better, and the spodumene beneficiation index after reuse is better. The proportions of the various components of the flocculants in Examples 4 to 5 are appropriately adjusted and changed within a preset range, and the effective treatment of spodumene beneficiation wastewater can be achieved, indicating that the proportions of the various components of the flocculants can be appropriately adjusted within a specific range. The present invention can effectively exert the synergistic effect of the various components in the flocculants by controlling the various components in the flocculants within a certain proportion range, and achieve effective treatment of spodumene beneficiation wastewater. The proportions of the various components of the flocculants in Comparative Examples 1 to 3 exceed the preset range, and compared with Example 1, the wastewater treatment effect and the reuse effect are both worse, indicating that the flocculant components in the present invention need to be controlled within a certain proportion range, and the dosage ratio of each component has an important influence on the wastewater effect.

[0079] Comparative Examples 4 and 5 use flocculants of other components, and the COD, SS, calcium ion and magnesium ion concentrations in their wastewater are significantly higher than those in Example 1. The recovery rate of spodumene crude concentrate after reuse is significantly lower than that in Example 1, indicating that the flocculant used in Example 1 has a good treatment effect on spodumene ore dressing wastewater.

[0080] The wastewater treatment processes in Comparative Examples 6 and 7 lack ultrasonic treatment and oxidation treatment processes, respectively. The COD, SS, calcium ion and magnesium ion concentrations in the wastewater are significantly higher than those in Example 1. The recovery rate of spodumene rough concentrate after reuse is 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 ore dressing wastewater.

[0081] In summary, the present application provides a method for treating and reusing spodumene ore dressing wastewater, which belongs to the field of ore dressing wastewater treatment. The present application prepares a composite polymer flocculant and adds it to the spodumene ore dressing wastewater, which can effectively capture the fine particles suspended in the wastewater and form larger flocs, thereby performing efficient flocculation and sedimentation; on this basis, the wastewater after flocculation and sedimentation is subjected to ultrasonic treatment and oxidation treatment in sequence, and the force field of the ultrasonic wave can be used to enhance the oxidation effect and increase the degradation rate of organic matter. Through the above-mentioned method, the present application can effectively reduce the chemical oxygen demand of spodumene ore dressing wastewater and the content of suspended matter, calcium ions, and magnesium ions in the wastewater with a simple process, less raw materials, and a shorter time, and the backwater obtained after treatment can be reused in the flotation process of spodumene, so as to achieve the recycling and zero discharge of spodumene ore dressing wastewater.

[0082] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for treating and reusing spodumene beneficiation wastewater, characterized in that: The steps include: S1. Prepare composite polymer flocculant; S2. Adding the composite polymer flocculant to the spodumene beneficiation wastewater for flocculation and sedimentation; S3. Ultrasonic treatment of the supernatant after flocculation and sedimentation; S4. adding an oxidant to the wastewater after ultrasonic treatment for oxidation treatment; S5. performing solid-liquid separation on the wastewater after the oxidation treatment, and recycling the separated liquid phase as return water to the flotation process of spodumene.

2. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S1, the composite polymer flocculant includes a first component, a second component and water; the first component includes sodium polyacrylate and / or polydimethyldiallylammonium chloride; the second component includes polydimethylaminopropyl methacrylamide and polyurethane.

3. The method for processing and reusing spodumene ore dressing wastewater according to claim 2, wherein: In the composite polymer flocculant, the mass fraction of the first component is 30% to 40%, the mass fraction of the polydimethylaminopropyl methacrylamide is 30% to 40%, the mass fraction of the polyurethane is 20% to 30%, and the mass fraction of water is 5% to 10%.

4. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S2, the added amount of the composite polymer flocculant is 5 to 15 mg / L.

5. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S2, the flocculation and sedimentation time is 20 to 40 minutes.

6. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S3, the frequency of the ultrasonic treatment is 20-30 kHz, and the power is 600-1000W.

7. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S3, the ultrasonic treatment time is 2 to 10 minutes.

8. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S4, the oxidant is hydrogen peroxide.

9. The method for processing and reusing spodumene ore dressing wastewater according to claim 1, wherein: In step S4, the dosage of the oxidant is 20-30 mg / L.

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

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