Recycling and treatment method of fluorite flotation wastewater

Abstract

The present disclosure relates to the technical field of flotation wastewater recycling and treatment, and provides a method for recycling and treating fluorite flotation wastewater, comprising: treating the fluorite flotation wastewater with a dilution of a microbial culture solution; wherein the microbial culture solution includes a fermentation solution of Bacillus subtilis ANSB060 and a fermentation solution of Lactobacillus plantarum GLM101, the deposit number of Bacillus subtilis ANSB060 being CGMCC No. 3440, and the deposit number of Lactobacillus plantarum GLM101 being CGMCC No. 11156. The recycling and treatment method provided by the present disclosure can significantly reduce the content of fluoride ions and suspended solids, total hardness, and chemical oxygen demand (COD) in fluorite flotation wastewater, has the advantages of low cost, high efficiency, and no risk of biological contamination, and has good prospects for large-scale application.

Description

Technical Field

[0001] The present disclosure relates to the technical field of flotation wastewater recovery and treatment, for example, to a method for recovering and treating fluorite flotation wastewater. Background Art

[0002] Fluorspar, also known as fluorspar, is primarily composed of calcium fluoride. Fluorspar concentrate is produced through flotation. Fluorspar has a wide range of uses and is a key raw material in various industries, including fluorine chemicals, metallurgy, glass, ceramics, and cement.

[0003] The CaF2 content in fluorite concentrate is usually required to be greater than 97%. In order to obtain high-quality fluorite concentrate, fluorite direct flotation is the most efficient and common separation technology. However, fluorite direct flotation produces a large amount of wastewater. According to statistics, the current water consumption required for direct flotation to process 1 ton of fluorite ore is 4~7m3. 3 .

[0004] Since fluorite (CaF2) often coexists with minerals with high calcium and magnesium ion content, such as calcite (CaCO3) and dolomite (CaMg(CO3)2), and fluorite, calcite and dolomite are typical salt minerals, in aqueous solution, the mineral lattice ions (Ca 2+ Mg 2+ 、F - 、 ) has high solubility, and the solution contains a large amount of dissolved F - , Ca 2+ Mg 2+ Ions are inevitable.

[0005] The wastewater generated by fluorite flotation mainly comes from the flotation, concentration and filtration processes. The wastewater is turbid and slightly yellow. The pH value of the flotation pulp is usually 4~7. In a weakly acidic environment, the solubility of minerals such as fluorite, calcite, and dolomite in the solution is further increased. The F in the flotation production water is - , Ca 2+ Mg 2+ The plasma content further increases. Furthermore, since fluorspar flotation collectors typically use fatty acids or modified fatty acids (e.g., saponified or sulfated fatty acids), and inhibitors typically use organic compounds such as dextrin, starch, tannin, tannic acid, and tannin extracts, the primary pollutants in fluorspar production wastewater include organic matter, high levels of fluoride, and other suspended solids. Therefore, untreated wastewater from fluorspar flotation (e.g., direct flotation) is not only difficult to recycle and reuse in the flotation process, but also easily pollutes river water quality and affects riverbank soil and plant growth if directly discharged. Therefore, treatment of fluorspar flotation wastewater (e.g., direct flotation wastewater) is essential, both from the perspectives of production economics and environmental protection.

[0006] For the recycling and treatment of mineral processing wastewater (e.g., fluorite flotation wastewater), the traditional method is primarily chemical precipitation, with research focused on developing new flocculants or chemical treatment methods. For example, Zhang Liye et al. developed a new coagulant in their "Coagulation and Sedimentation Treatment of Fluorite Direct Flotation Wastewater Project" that achieved 100% wastewater recovery. The coagulant was primarily a complex formulation of calcium, magnesium, and manganese salts. Another example, Jiang Ying's "Research on the Treatment of Fluorine-Containing Mineral Processing Wastewater Using a Chemical Precipitation-Adsorption Composite Process" utilized a chemical precipitation-adsorption composite process to treat fluorine-containing mineral processing wastewater and investigated the effectiveness of different adsorbents and precipitants in removing fluorine. Furthermore, Liu Wenli et al.'s "Research and Application of Bayan Obo Mine Wastewater Treatment Technology" improved wastewater quality by dosing 0.175 mg / L of polyferric sulfate and 0.054 mg / L of polyacrylamide. However, chemical treatment processes are time-consuming, inefficient, and costly.

[0007] In recent years, research has gradually shifted to using biological agents to treat mineral processing wastewater (e.g., fluorite flotation wastewater). For example, Changsha Saiens Environmental Protection Technology Co., Ltd. and Min Xiaobo et al. from Central South University jointly developed a biological agent in Chinese patent document CN104478160B. This biological agent is primarily composed of Thiobacillus ferrooxidans, Thiobacillus thiooxidans, and iron salts. The biological agent, in combination with an oxidant, can directly remove heavy metal ions, organic matter, and calcium and magnesium ions from wastewater. Another example is Hu Xuewei et al. from Kunming University of Science and Technology, in Chinese patent document CN105800796B, proposed a biological treatment process for flotation wastewater. This process utilizes co-metabolites of the biological bacteria to react with heavy metal ions in the flotation wastewater to form metal sulfide precipitates. The reaction time of this process is significantly shorter than that of traditional processes. For example, Liu Xingyu and others from Youyan Engineering Technology Research Institute Co., Ltd. developed a Bacillus sp. in Chinese patent document CN105779327B that can reduce the pH of flotation wastewater by fermenting and producing organic acids. In another example, Chen Shaohua and others from South-Central University for Nationalities used Shewanella Oneida in Chinese patent document CN109574407B to develop a biological method for the efficient removal of butyl xanthate and the heavy metal Cr(VI) from flotation wastewater.

[0008] As previously mentioned, while the use of biological agents to treat mineral processing wastewater offers advantages such as high efficiency, low cost, and short reaction times, relatively few successful biological treatment methods have been developed. This may be due to limited research into which bacterial strains can absorb or degrade relevant components in mineral processing wastewater, or which bacterial strains' metabolites can flocculate and precipitate with these components. More importantly, currently known biological treatment methods typically require direct contact between the biological agent and the wastewater, supplementing the wastewater with nutrients to enable the growth and proliferation of the bacteria in the biological agent, and the continuous production of metabolites to remove the relevant components. However, while these biological treatment methods have some water purification effects, they also introduce a new pollutant—biological contamination. Specifically, most bacteria are toxic and should not be exposed to humans or animals. Furthermore, bacteria are prone to mutating in complex environments, resulting in unpredictable variants. Therefore, from the perspective of preventing and controlling biological contamination, current biological treatment methods for mineral processing wastewater (e.g., fluorite flotation wastewater) present significant safety risks and are not suitable for large-scale implementation.

[0009] In summary, there is an urgent need for a biological treatment method with high efficiency in purifying fluorite flotation wastewater (e.g., fluorite positive flotation wastewater) so that the method can avoid the generation of biological contamination and has the advantages of low cost, high efficiency and no biological contamination risk. Summary of the Invention

[0010] The purpose of the present disclosure is to overcome the shortcomings of the chemical treatment method in the prior art, such as the time-consuming, low-efficiency and high-cost treatment process, and the high potential for biological contamination safety and difficulty in biological contamination risk prevention and control of the biological treatment method, and to provide a fluorite flotation wastewater recovery and treatment method, so as to at least significantly reduce the fluoride ion and suspended solids content, total hardness and chemical oxygen demand (COD) in the fluorite flotation wastewater, with the advantages of low cost, high efficiency and no biological contamination risk, and good prospects for large-scale application.

[0011] The purpose of this disclosure is achieved through the following technical solutions:

[0012] On the one hand, a method for recycling and treating fluorite flotation wastewater is provided. The recycling and treating method comprises: treating the fluorite flotation wastewater with a dilution of a microbial culture solution; wherein the microbial culture solution comprises Bacillus subtilis ( Bacillus subtilis )ANSB060 fermentation broth and Lactobacillus plantarum ( Lactobacillus plantarum ) GLM101 fermentation broth, the preservation number of the Bacillus subtilis ANSB060 is CGMCC No.3440, and the preservation number of the Lactobacillus plantarum GLM101 is CGMCC No.11156.

[0013] After research, the inventors of the present disclosure found that when the fluorite flotation wastewater is recycled and treated, the fermentation liquid of the Bacillus subtilis ANSB060 and the fermentation liquid of the Lactobacillus plantarum GLM101 in the microbial liquid can produce a synergistic effect, so that the diluted liquid of the microbial liquid can effectively recycle and treat the fluorite flotation wastewater.

[0014] It should be noted that the contribution of the present disclosure also lies in the discovery that the Bacillus subtilis ANSB060 and the Lactobacillus plantarum GLM101 can be used for the recovery and treatment of fluorite flotation wastewater, while the prior art only discloses that the Bacillus subtilis ANSB060 and the Lactobacillus plantarum GLM101 can be used to prepare feed and / or feed additives. In this regard, it is obvious that the use of the Bacillus subtilis ANSB060 and the Lactobacillus plantarum GLM101 in the recovery and treatment of fluorite flotation wastewater is completely different from the use of the Bacillus subtilis ANSB060 and the Lactobacillus plantarum GLM101 in the preparation of feed and / or feed additives.

[0015] In some embodiments, the fermentation broth of Bacillus subtilis ANSB060 has a bacterial concentration of 1×10 6 cfu / mL.

[0016] In some embodiments, the fermentation broth of Lactobacillus plantarum GLM101 has a bacterial concentration of 1×10 6 cfu / mL.

[0017] In some embodiments, the volume ratio of the fermentation broth of Bacillus subtilis ANSB060 to the fermentation broth of Lactobacillus plantarum GLM101 is 2-4:6-8.

[0018] In some embodiments, the method for preparing the diluted solution of the microbial liquid comprises: centrifuging the microbial liquid to separate the cells to obtain a supernatant; and diluting the supernatant to 500 to 800 times to obtain the diluted solution of the microbial liquid.

[0019] In some examples, the dilution is performed using distilled water.

[0020] In some embodiments, the treatment of the fluorite flotation wastewater with a diluted solution of the microbial culture comprises: uniformly mixing an alkaline reagent with the fluorite flotation wastewater, performing a first standing and a first pressure filtration to obtain a filtrate; and uniformly mixing the diluted solution of the microbial culture with the filtrate, performing a second standing and a second pressure filtration.

[0021] It should be noted that the pH of the fluorite flotation wastewater is about 4-7. In some of the above embodiments, by uniformly mixing the alkaline reagent with the fluorite flotation wastewater, the acid in the fluorite flotation wastewater can be better neutralized, thereby achieving better removal of Ca in the fluorite flotation wastewater. 2+ Mg 2+ The effects of ions are inevitable.

[0022] In some embodiments, the final concentration of the alkaline agent is 0.5-1 M, and the alkaline agent includes at least one of sodium hydroxide and sodium carbonate.

[0023] In some embodiments, the first standing temperature is 20-40° C., and the first standing time is 10-20 minutes.

[0024] In some embodiments, the volume ratio of the filtrate to the dilution of the microbial culture liquid is 1:1-10.

[0025] In some examples, the volume ratio of the filtrate to the dilution of the microbial culture liquid is 1:1.

[0026] In some embodiments, the second standing temperature is 25-35° C., and the second standing time is 20-30 minutes.

[0027] In some embodiments, the fluorite flotation wastewater includes fluorite positive flotation wastewater, and the fluorite positive flotation wastewater contains fluoride ions, calcium ions, magnesium ions, organic matter and suspended matter.

[0028] In some embodiments, in the fluorite flotation wastewater, the fluoride ion content is not less than 900 mg / L, the total hardness calculated based on the total content of the calcium ions and the magnesium ions is not less than 1200 mg / L, the chemical oxygen demand of the organic matter is not less than 500 mg / L, and the suspended matter content is not less than 70,000 mg / L.

[0029] In some embodiments, the fluorite direct flotation wastewater is wastewater obtained through fluorite direct flotation; wherein, the fluorite direct flotation uses fatty acids or modified fatty acids as collectors, water glass, acidified water glass or salinized water glass as dispersants, and tannins, tannin extracts, tannic acid, starch or dextrin as inhibitors.

[0030] It should be noted that the modified fatty acid is obtained by modifying the fatty acid; wherein the modification may be, for example, saponification or sulfation.

[0031] In some examples, the fatty acid includes oleic acid.

[0032] In some examples, the modified fatty acid includes modified oleic acid.

[0033] It is worth noting that the recovery and treatment method provided in the present disclosure can significantly reduce the content of fluoride ions and suspended matter, total hardness and chemical oxygen demand (COD) in the fluorite flotation wastewater in a very short time. After being treated by the recovery and treatment method, the content of related substances in the fluorite flotation wastewater is low, which is far better than the recycling and reuse standards.

[0034] Furthermore, based on the state of the art, the recovery and treatment method provided by the present disclosure has a significantly shorter treatment time than traditional chemical precipitation methods, typically taking more than one hour. Furthermore, compared to other biological treatment methods, the recovery and treatment method provided by the present disclosure utilizes only a dilution of the microbial broth (i.e., the fermentation broth of Bacillus subtilis ANSB060 and the fermentation broth of Lactobacillus plantarum GLM101) to recover and treat the fluorite flotation wastewater. This requires significantly less fermentation broth, thus avoiding the generation of biological contamination and eliminating the risk of biological contamination. Therefore, the recovery and treatment method provided by the present disclosure has the advantages of low cost, high efficiency, and no risk of biological contamination.

[0035] The beneficial effects of the present disclosure are:

[0036] The present invention discloses a method for recycling and treating fluorite flotation wastewater, which can significantly reduce the content of fluoride ions and suspended solids, total hardness and chemical oxygen demand (COD) in fluorite flotation wastewater. It has the advantages of low cost, high efficiency and no biological contamination risk, and has good prospects for large-scale application. DETAILED DESCRIPTION

[0037] The following is a clear and complete description of the technical solutions in some embodiments of the present disclosure. Obviously, the embodiments described are only some of the embodiments of the present disclosure, not all of them. Based on the embodiments provided by the present disclosure, all other embodiments obtained by ordinary technicians in this field are within the scope of protection of the present disclosure.

[0038] In the following, the terms "first," "second," etc. are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the quantity of the technical features indicated. Therefore, a feature specified as "first," "second," etc. may explicitly or implicitly include one or more of the features.

[0039] When describing some embodiments, the expression "A and / or B" may be used. It is easy to understand that "A and / or B" includes the following three combinations: only A, only B, and a combination of A and B.

[0040] When describing some embodiments, the expressions "at least one of A, B and C" and "at least one of A, B or C" may be used, both of which have the same meaning and include the following combinations of A, B and C: only A, only B, only C, the combination of A and B, the combination of A and C, the combination of B and C, and the combination of A, B and C.

[0041] It should be understood that the Bacillus subtilis ANSB060 and Lactobacillus plantarum GLM101 used in the examples of this disclosure are both publicly available biological materials. Bacillus subtilis ANSB060 has a deposit number of CGMCC No. 3440 and has been published in multiple Chinese patent documents (e.g., CN201010129783.5). Lactobacillus plantarum GLM101 has a deposit number of CGMCC No. 11156 and has been published in multiple Chinese patent documents (e.g., CN201510559899.5).

[0042] It should be noted that in Tables 1 to 11 of the embodiments of the present disclosure, total hardness is calculated as the total content of calcium ions and magnesium ions, and COD is the chemical oxygen demand measured using potassium dichromate (K2Cr2O7) as an oxidant.

[0043] Example 1

[0044] 1. Raw materials

[0045] Bacillus subtilis ANSB060, deposited under CGMCC No. 3440;

[0046] Lactobacillus plantarum GLM101, deposited under CGMCC No. 11156;

[0047] Sodium hydroxide and sodium carbonate were commercially available.

[0048] LB liquid culture medium, self-prepared, formula: tryptone 10 g / L, yeast extract 5 g / L, sodium chloride (NaCl) 10 g / L.

[0049] 2. A method for preparing a dilution of a microbial culture solution, comprising:

[0050] S100. Bacillus subtilis ANSB060 was cultured in LB liquid medium to a bacterial concentration of 1×10 6 cfu / mL, and the fermentation broth of Bacillus subtilis ANSB060 was obtained;

[0051] S200. Lactobacillus plantarum GLM101 was cultured in LB liquid medium to a bacterial concentration of 1×10 6cfu / mL, and the fermentation broth of Lactobacillus plantarum GLM101 was obtained;

[0052] S300 according to a volume ratio of 2.5: 7.5 Bacillus subtilis ANSB060 fermentation broth and Lactobacillus plantarum GLM101 was mixed to obtain a microbial culture;

[0053] S400. The microbial culture was centrifuged to separate the cells and the supernatant was filtered;

[0054] S500. Dilute the supernatant to 800 times with distilled water.

[0055] 3. Fluorite positive flotation wastewater

[0056] Fluorite was positively floated using a flotation reagent system that used modified oleic acid as a collector, acidified water glass as a dispersant, and tannin as an inhibitor. Fluorite positive flotation wastewater was collected, and the contents of related substances in the wastewater are shown in Table 1.

[0057] 4. Fluorite flotation wastewater recovery and treatment methods, including:

[0058] S1. Add sodium hydroxide to the fluorite flotation wastewater to a final concentration of 1 M, stir evenly, and allow to stand at 30-32°C for 10 minutes. Press filter to obtain a filtrate.

[0059] S2. Mix the filtrate and the diluted microbial culture solution in a volume ratio of 1:10. Stir thoroughly, let it stand at 30-32°C for 20 minutes, and filter press to obtain the treated solution.

[0060] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 2.

[0061] Example 2

[0062] The raw materials and fluorite flotation wastewater used in this example are the same as those in Example 1.

[0063] 1. A method for preparing a dilution of a microbial culture solution, comprising:

[0064] S100. Bacillus subtilis ANSB060 was cultured in LB liquid medium to a bacterial concentration of 1×10 6 cfu / mL, and the fermentation broth of Bacillus subtilis ANSB060 was obtained;

[0065] S200. Lactobacillus plantarum GLM101 was cultured in LB liquid medium to a bacterial concentration of 1×10 6cfu / mL, and the fermentation broth of Lactobacillus plantarum GLM101 was obtained;

[0066] S300 according to a volume ratio of 3: 7 Bacillus subtilis ANSB060 fermentation broth and Lactobacillus plantarum GLM101 was mixed to obtain a microbial culture;

[0067] S400. The microbial culture was centrifuged to separate the cells and the supernatant was filtered;

[0068] S500. Dilute the supernatant to 500 times with distilled water.

[0069] 2. Fluorite flotation wastewater recovery and treatment methods, including:

[0070] S1. Sodium carbonate was added to the fluorite flotation wastewater to a final concentration of 0.5 M. After stirring, the mixture was allowed to stand at 20-22°C for 20 minutes and then filtered to obtain a filtrate.

[0071] S2. Mix the filtrate and the diluted microbial culture solution in a volume ratio of 1:5. Stir thoroughly, let it stand at 25-26°C for 30 minutes, and filter press to obtain the treated solution.

[0072] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 3.

[0073] Example 3

[0074] The raw materials and fluorite flotation wastewater used in this example are the same as those in Example 1.

[0075] 1. A method for preparing a dilution of a microbial culture solution, comprising:

[0076] S100. Bacillus subtilis ANSB060 was cultured in LB liquid medium to a bacterial concentration of 1×10 6 cfu / mL, and the fermentation broth of Bacillus subtilis ANSB060 was obtained;

[0077] S200. Lactobacillus plantarum GLM101 was cultured in LB liquid medium to a bacterial concentration of 1×10 6 cfu / mL, and the fermentation broth of Lactobacillus plantarum GLM101 was obtained;

[0078] S300 according to a volume ratio of 3: 8 Bacillus subtilis ANSB060 fermentation broth and Lactobacillus plantarum GLM101 was mixed to obtain a microbial culture;

[0079] S400. The microbial culture was centrifuged to separate the cells and the supernatant was filtered;

[0080] S500. Dilute the supernatant to 600 times with distilled water.

[0081] 2. Fluorite flotation wastewater recovery and treatment methods, including:

[0082] S1. Sodium carbonate was added to the fluorite flotation wastewater to a final concentration of 0.5 M. After stirring, the mixture was allowed to stand at 38-40°C for 15 minutes and then filtered to obtain a filtrate.

[0083] S2. Mix the filtrate and the diluted microbial culture solution in a 1:1 volume ratio. Stir thoroughly and allow to stand at 33-35°C for 25 minutes. Press filter to obtain the treated solution.

[0084] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 4.

[0085] Blank control example

[0086] The recycling and treatment method of fluorite flotation wastewater of the blank control example was compared with the recycling and treatment method of fluorite flotation wastewater of Example 3. The difference between the blank control example and Example 3 is that:

[0087] In S2, no dilution of the microbial culture solution was used;

[0088] Other conditions, such as the fluorite flotation wastewater used, the selection of the remaining reagents, the dosage of the reagents, and the process flow, are the same as those in Example 3 (compared with Example 3, this blank control example does not use a dilution of the microbial liquid to prove that the recovery and treatment method disclosed in the present invention is more effective).

[0089] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 5.

[0090] According to the above results, it can be seen that in the blank control example, the diluted solution of microbial culture was not used to recycle the fluorite flotation wastewater. Compared with the fluorite flotation wastewater, the content of fluoride ions and suspended matter, total hardness and COD in the obtained treated liquid were reduced, but they were not effectively reduced. The obtained treated liquid could not be directly discharged or recovered and used for fluorite flotation.

[0091] Comparative Example 1

[0092] The recovery and treatment method of fluorite flotation wastewater of Control Example 1 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 1 and Example 3 is that:

[0093] In S2, the diluted solution of the microbial culture is replaced with a mixture of the diluted solution of the culture and an iron salt; wherein the culture is obtained by culturing Thiobacillus ferrooxidans and Thiobacillus thiooxidans according to the method described in Example 1 of Chinese patent document CN104478160B; the diluted solution of the culture is obtained by diluting the supernatant obtained after centrifuging the culture to separate the bacteria by 600 times; and the diluted solution of the culture is mixed with the iron salt according to the method described in Example 1 of Chinese patent document CN104478160B;

[0094] Other conditions, such as the fluorite flotation wastewater used, the selection of the remaining reagents, the dosage of the reagents, and the process flow, are the same as those in Example 3 (compared with Example 3, this control example uses a mixture of the diluted bacterial liquid and the iron salt in the prior art for recovery treatment to prove that the recovery treatment method disclosed in the present invention is more effective).

[0095] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 6.

[0096] According to the above results, it can be seen that, considering the factors of avoiding biological contamination risks and reducing process costs, if the bacterial solution of Control Example 1 is diluted and the mixture of the obtained bacterial solution dilution and iron salt is used to recycle the fluorite flotation wastewater, compared with the blank control example, the fluoride ion and suspended matter content, total hardness and COD in the obtained treated liquid are reduced, but still cannot be effectively reduced, and the obtained treated liquid still cannot be directly discharged or recovered and used for fluorite flotation.

[0097] Comparative Example 2

[0098] The recovery and treatment method of fluorite flotation wastewater of Control Example 2 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 2 and Example 3 is that:

[0099] The microbial culture solution only includes the bacterial concentration of 1×10 6 cfu / mL of fermentation broth of Bacillus subtilis ANSB060;

[0100] Other conditions, such as the fluorite positive flotation wastewater used, the method for preparing the dilution of the microbial culture solution, the selection of the remaining reagents, the dosage of the reagents, and the process flow, were the same as those in Example 3 (compared with Example 3, this control example did not include the fermentation liquid of Lactobacillus plantarum GLM101 in the microbial culture solution, to demonstrate that the recovery and treatment method disclosed herein is more effective).

[0101] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 7.

[0102] According to the above results, it can be seen that in Control Example 2, a dilution of a microbial culture liquid containing only the fermentation liquid of Bacillus subtilis ANSB060 is used to recycle fluorite flotation wastewater. Compared with the blank control example, the fluoride ion and suspended solids content, total hardness, and COD in the treated liquid obtained in Control Example 2 are reduced, but still fail to be effectively reduced, and the treated liquid still cannot be directly discharged or recycled and used for fluorite flotation. On this basis, since the dilution multiple and dosage of the dilution of the microbial culture liquid in Control Example 2 are equal to those in Example 3, the recovery and treatment method of Example 3, which uses a microbial culture liquid containing both the fermentation liquid of Bacillus subtilis ANSB060 and the fermentation liquid of Lactobacillus plantarum GLM101, has a more excellent effect in reducing the content of fluoride ions and suspended solids, total hardness, and COD than the recovery and treatment method of Control Example 2, which uses a microbial culture liquid containing both the fermentation liquid of Bacillus subtilis ANSB060 and the fermentation liquid of Lactobacillus plantarum GLM101.

[0103] Comparative Example 3

[0104] The recovery and treatment method of fluorite flotation wastewater of Control Example 3 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 3 and Example 3 is that:

[0105] The microbial culture solution only includes the bacterial concentration of 1×10 6 cfu / mL of fermentation broth of Lactobacillus plantarum GLM101;

[0106] Other conditions, such as the fluorite positive flotation wastewater used, the method for preparing the dilution of the microbial culture solution, the selection of the remaining reagents, the dosage of the reagents, and the process flow, were the same as those in Example 3 (compared with Example 3, the microbial culture solution in this control example did not include the fermentation liquid of Bacillus subtilis ANSB060, which is used to prove that the recovery and treatment method disclosed in the present invention is more effective).

[0107] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 8.

[0108] According to the above results, it can be seen that the control example 3 uses a dilution of a microbial bacterial liquid comprising only the fermentation liquid of Lactobacillus plantarum GLM101 to recycle the fluorite flotation wastewater. Compared with the blank control example, the content of fluoride ions and suspended solids and COD in the treatment liquid obtained in the control example 3 are reduced, but still fail to be effectively reduced, and the total hardness of the treatment liquid is increased, and the treatment liquid still cannot be directly discharged or recycled and used for fluorite flotation. On this basis, since the dilution multiple and the dosage of the dilution of the microbial bacterial liquid in the control example 3 are equal to those in Example 3, the recovery and treatment method of Example 3 uses a microbial bacterial liquid comprising only the fermentation liquid of Lactobacillus plantarum GLM101, and the recovery and treatment method of Example 3 uses a microbial bacterial liquid comprising both the fermentation liquid of Bacillus subtilis ANSB060 and the fermentation liquid of Lactobacillus plantarum GLM101. It has a more excellent effect in reducing the content of fluoride ions and suspended solids, total hardness and COD.

[0109] It should be noted that, under the conditions that the dilution multiple and the dosage of the diluent of the microbial liquid are equal, in terms of reducing the content of fluoride ions and suspended solids, total hardness and COD, whether it is the microbial liquid of Control Example 2 comprising only the fermentation liquid of Bacillus subtilis ANSB060, or the microbial liquid of Control Example 3 comprising only the fermentation liquid of Lactobacillus plantarum GLM101, the effect is not as good as the microbial liquid of Example 3 comprising both the fermentation liquid of Bacillus subtilis ANSB060 and the fermentation liquid of Lactobacillus plantarum GLM101. This shows that in the microbial liquid provided in the embodiments of the present disclosure (e.g., Example 3), Bacillus subtilis ANSB060 and Lactobacillus plantarum GLM101 produce a synergistic effect when recycling and treating fluorite flotation wastewater (e.g., fluorite positive flotation wastewater).

[0110] Comparative Example 4

[0111] The recovery and treatment method of fluorite flotation wastewater of Control Example 4 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 4 and Example 3 is that:

[0112] The bacterial concentration of the microbial solution was 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis ANSB060 was replaced with a bacterial concentration of 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis CMCC 63501 (from China Center for Medical Microbiological Culture Collection);

[0113] Other conditions, such as the fluorite flotation wastewater used, the method for preparing the dilution solution of the microbial culture, the selection of the remaining reagents, the dosage of the reagents, and the process flow, were the same as those in Example 3 (compared with Example 3, this control example replaced the fermentation broth of Bacillus subtilis ANSB060 with the fermentation broth of other Bacillus subtilis to demonstrate that the recovery and treatment method disclosed herein is more effective).

[0114] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 9.

[0115] According to the above results, it can be seen that the bacterial concentration in the control example 4 is 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis ANSB060 was replaced with a bacterial concentration of 1×10 6 cfu / mL of the fermentation liquid of Bacillus subtilis CMCC 63501 was used to recycle fluorite flotation wastewater. Compared with the blank control example, the fluoride ion and suspended matter content, total hardness and COD in the treated liquid obtained in Control Example 4 were reduced. However, compared with Example 3, the fluoride ion and suspended matter content, total hardness and COD in the treated liquid obtained in Control Example 4 were significantly increased. The obtained treated liquid still could not be directly discharged or recycled and used for fluorite flotation. It can be seen that although a good effect can be achieved when the diluted liquid of the microbial culture prepared by co-preparing the fermentation liquid of Bacillus subtilis ANSB060 and the fermentation liquid of Lactobacillus plantarum GLM101 is used to recycle fluorite flotation wastewater, this effect cannot be achieved if Bacillus subtilis ANSB060 is replaced by other Bacillus subtilis. Therefore, the good recovery and treatment effect of the microbial liquid provided in the embodiments of the present disclosure (for example, Example 3) on fluorite flotation wastewater (for example, fluorite positive flotation wastewater) is achieved by utilizing the synergistic effect produced by Bacillus subtilis ANSB060 and Lactobacillus plantarum GLM101, and not all Bacillus subtilis can produce this synergistic effect with Lactobacillus plantarum GLM101.

[0116] Comparative Example 5

[0117] The recovery and treatment method of fluorite flotation wastewater of Control Example 5 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 5 and Example 3 is that:

[0118] The bacterial concentration of the microbial solution was 1×10 6 cfu / mL of Lactobacillus plantarum GLM101 was replaced with a fermentation broth with a bacterial concentration of 1×10 6cfu / mL of fermentation broth of Lactobacillus plantarum DSM 13273 (from the German Collection of Microorganisms);

[0119] Other conditions, such as the fluorite flotation wastewater used, the method for preparing the dilution of the microbial culture, the selection of the remaining reagents, the dosage of the reagents, and the process flow, were the same as those in Example 3 (compared with Example 3, this control example replaced the fermentation liquid of Lactobacillus plantarum GLM101 with the fermentation liquid of other Lactobacillus plantarum to demonstrate that the recovery and treatment method disclosed herein is more effective).

[0120] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 10.

[0121] According to the above results, it can be seen that in control example 5, the bacterial concentration of the microbial solution was 1×10 6 cfu / mL of Lactobacillus plantarum GLM101 was replaced with a fermentation broth with a bacterial concentration of 1×10 6 cfu / mL of the fermentation liquid of Lactobacillus plantarum DSM 13273 was used to recycle fluorite flotation wastewater. Compared with the blank control example, the content of fluoride ions and suspended matter, total hardness and COD in the treated liquid obtained in Control Example 5 were all reduced. However, compared with Example 3, the content of fluoride ions and suspended matter, total hardness and COD in the treated liquid obtained in Control Example 5 were significantly increased. However, the treated liquid still could not be directly discharged or recycled and used for fluorite flotation. It can be seen that although a good effect can be achieved when the dilution of the microbial bacterial liquid prepared by co-preparing the fermentation liquid of Lactobacillus plantarum GLM101 and the fermentation liquid of Bacillus subtilis ANSB060 is used to recycle fluorite flotation wastewater, this effect cannot be achieved if Lactobacillus plantarum GLM101 is replaced by other Lactobacillus plantarum. Therefore, the good recovery and treatment effect of the microbial liquid provided in the embodiments of the present disclosure (for example, Example 3) on fluorite flotation wastewater (for example, fluorite positive flotation wastewater) is achieved by utilizing the synergistic effect produced by Lactobacillus plantarum GLM101 and Bacillus subtilis ANSB060, and not all Lactobacillus plantarum can produce this synergistic effect with Bacillus subtilis ANSB060.

[0122] Comparative Example 6

[0123] The recovery and treatment method of fluorite flotation wastewater of Control Example 6 is compared with the recovery and treatment method of fluorite flotation wastewater of Example 3. The difference between Control Example 6 and Example 3 is that:

[0124] The bacterial concentration of the microbial solution was 1×10 6cfu / mL of the fermentation broth of Bacillus subtilis ANSB060 was replaced with a bacterial concentration of 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis CMCC 63501 (from China Center for Medical Microbiological Culture Collection);

[0125] The bacterial concentration of the microbial solution was 1×10 6 cfu / mL of Lactobacillus plantarum GLM101 was replaced with a fermentation broth with a bacterial concentration of 1×10 6 cfu / mL of fermentation broth of Lactobacillus plantarum DSM 13273 (from the German Collection of Microorganisms);

[0126] Other conditions, such as the fluorite positive flotation wastewater used, the method for preparing the dilution of the microbial culture, the selection of the remaining reagents, the dosage of the reagents, and the process flow, are the same as those in Example 3 (compared with Example 3, this control example replaces the fermentation liquid of Bacillus subtilis ANSB060 with the fermentation liquid of other Bacillus subtilis, and replaces the fermentation liquid of Lactobacillus plantarum GLM101 with the fermentation liquid of other Lactobacillus plantarum, to prove that the recovery and treatment method disclosed herein is more effective).

[0127] The treatment liquid obtained by the above recovery treatment method was tested for the content of relevant substances, and the results are shown in Table 11.

[0128] According to the above results, it can be seen that the bacterial concentration in the control example 6 is 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis ANSB060 and the bacterial concentration was 1×10 6 cfu / mL of Lactobacillus plantarum GLM101 were replaced with a bacterial concentration of 1×10 6 cfu / mL of the fermentation broth of Bacillus subtilis CMCC 63501 and the bacterial concentration was 1×10 6 cfu / mL of the fermentation liquid of Lactobacillus plantarum DSM 13273 was used to recycle the fluorite flotation wastewater. Compared with the blank control example, the fluoride ion and suspended matter content, total hardness and COD in the treated liquid obtained in Control Example 6 were reduced, but still failed to be effectively reduced. The treated liquid obtained could not be directly discharged or recovered and used for fluorite flotation; at the same time, compared with Control Example 4, the fluoride ion and suspended matter content and total hardness in the treated liquid obtained in Control Example 6 were reduced, but the COD was increased; compared with Control Example 5, the fluoride ion and suspended matter content in the treated liquid obtained in Control Example 6 were reduced, but the total hardness and COD were increased.

[0129] Therefore, the recycling and treatment method of fluorite flotation wastewater disclosed in the present invention can at least significantly reduce the content of fluoride ions and suspended matter, total hardness and COD in fluorite flotation wastewater, has the advantages of low cost, high efficiency and no biological contamination risk, and has good prospects for large-scale application.

[0130] The foregoing description is merely a preferred embodiment of the present disclosure. It should be understood that the present disclosure is not limited to the form disclosed herein and should not be construed as excluding other embodiments. Rather, the present disclosure is applicable to various other combinations, modifications, and environments and can be modified within the scope of the concepts described herein through the above teachings or techniques or knowledge in the relevant fields. Modifications and variations made by those skilled in the art that do not depart from the spirit and scope of the present disclosure are intended to be protected by the claims appended hereto.

Claims

1. A method for recycling and treating fluorite flotation wastewater, characterized in that: include: Treating the fluorite flotation wastewater with a diluted solution of microbial culture liquid; Wherein, the microbial liquid includes Bacillus subtilis ( Bacillus subtilis )ANSB060 fermentation broth and Lactobacillus plantarum ( Lactobacillus plantarum ) GLM101 fermentation broth, the preservation number of the Bacillus subtilis ANSB060 is CGMCC No.3440, and the preservation number of the Lactobacillus plantarum GLM101 is CGMCC No.11156.

2. The recycling method according to claim 1, characterized in that: The bacterial concentration of the fermentation broth of Bacillus subtilis ANSB060 is 1×10 6 cfu / mL; And / or, the fermentation broth of Lactobacillus plantarum GLM101 has a bacterial concentration of 1×10 6 cfu / mL.

3. The recycling method according to claim 2, characterized in that: The volume ratio of the fermentation broth of Bacillus subtilis ANSB060 to the fermentation broth of Lactobacillus plantarum GLM101 is 2-4:6-8.

4. The recycling method according to claim 3, characterized in that: The method for preparing the dilution of the microbial liquid comprises: centrifuging the microbial culture to separate the cells and obtain a supernatant; and The supernatant is diluted to 500-800 times to obtain a dilution of the microbial culture liquid.

5. The recycling method according to any one of claims 1 to 4, characterized in that: The method of treating the fluorite flotation wastewater with a diluted solution of a microbial bacterial solution comprises: taking an alkaline reagent and uniformly mixing the fluorite flotation wastewater, performing a first standing and a first pressure filtration to obtain a filtrate; and The diluted liquid of the microbial culture liquid is mixed evenly with the filtrate, and a second standing and a second pressure filtration are performed.

6. The recycling method according to claim 5, characterized in that: The final concentration of the alkaline reagent is 0.5-1 M, and the alkaline reagent includes at least one of sodium hydroxide and sodium carbonate; And / or, the first standing temperature is 20-40° C., and the first standing time is 10-20 minutes.

7. The recycling method according to claim 5, characterized in that: The volume ratio of the filtrate to the dilution of the microbial culture liquid is 1:1-10; And / or, the second standing temperature is 25-35° C., and the second standing time is 20-30 min.

8. The recycling method according to claim 1, characterized in that: The fluorite flotation wastewater includes fluorite positive flotation wastewater, and the fluorite positive flotation wastewater contains fluoride ions, calcium ions, magnesium ions, organic matter and suspended matter.

9. The recycling method according to claim 8, characterized in that: In the fluorite flotation wastewater, the fluoride ion content is not less than 900 mg / L, the total hardness calculated based on the total content of the calcium ions and the magnesium ions is not less than 1200 mg / L, the chemical oxygen demand of the organic matter is not less than 500 mg / L, and the suspended matter content is not less than 70,000 mg / L.

10. The recycling method according to claim 8, characterized in that: The fluorite direct flotation wastewater is wastewater obtained through fluorite direct flotation; wherein, the fluorite direct flotation uses fatty acid or modified fatty acid as a collector, uses water glass, acidified water glass or salinized water glass as a dispersant, and uses tannin, tannin extract, tannic acid, starch or dextrin as an inhibitor.

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