A method for efficiently solidifying manganese in the leaching solution of manganese slag based on microorganisms and a cultivation method

Abstract

The present invention provides a method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms and a cultivation method; the method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms includes the steps: S1, obtaining manganese slag leaching solution and bacterial solution; the manganese slag leaching solution contains divalent manganese, and the bacterial solution contains Klebsiella; S2, mixing calcium acetate and the bacterial solution into the manganese slag leaching solution to obtain a culture solution; culturing the culture solution for at least 30 h to obtain a reaction solution; S3, performing solid-liquid separation on the reaction solution to obtain a manganese-removed separation solution. The present invention can effectively improve the solidification effect of Mn(II) in electrolytic manganese slag leaching solution by combining Klebsiella and calcium acetate.

Description

Technical Field

[0001] The present invention relates to the field of water treatment, and particularly to a method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms and a cultivation method. Background Art

[0002] Metallic manganese (Mn), as an important industrial raw material, is widely used in fields such as iron and steel metallurgy, aerospace, consumer electronics, food chemistry, and military defense, and is an important strategic resource in China. The electrolysis method is a relatively mature process for producing metallic manganese at present. This method can produce high-purity (99.5%) elemental manganese and is the mainstream process for producing metallic manganese in China at present. With the expansion of electrolytic manganese production capacity, a large amount of smelting waste residue - electrolytic manganese residue (EMR) is generated accordingly. It is statistically shown that 9 - 12 tons of electrolytic manganese residue will be produced for every 1 ton of metallic manganese produced. Open-air stacking is the main treatment method for electrolytic manganese residue at present. This not only occupies a large amount of land area, but also the residual ammonia nitrogen and heavy metal ions in the manganese residue will continuously aggravate the damage to the environment over time.

[0003] Electrolytic manganese residue (EMR) contains a large amount of soluble Mn(II), and due to its good water solubility, it is very easy to enter the natural environment through rainwater scouring, forming manganese slag leaching solution. The disordered discharge of manganese will bring serious pollution problems; high-concentration Mn has strong toxicity, which will not only inhibit the absorption of Fe by the human body, but also damage the blood system, liver, heart, and nervous system.

[0004] At present, the treatment methods for divalent manganese leaching solution mainly include physical methods, chemical methods, and biological methods. Among them, the biological method has the advantages of small material disturbance, high solidification efficiency, environmental friendliness, and no secondary pollution, and has developed relatively rapidly. However, only using microorganisms to solidify Mn(II) in manganese leaching solution cannot achieve the efficient removal of Mn(II).

[0005] In view of this, it is necessary to provide a method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms and a cultivation method to solve or at least alleviate the technical defect of how to efficiently solidify manganese in manganese slag leaching solution based on microorganisms. Summary of the Invention

[0006] The main object of the present invention is to provide a method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms and a cultivation method, aiming to solve the above technical problem of how to efficiently solidify manganese in manganese slag leaching solution based on microorganisms.

[0007] To achieve the above object, the present invention provides a method for efficiently solidifying manganese in manganese slag leaching solution based on microorganisms, including the steps of:

[0008] S1, obtaining manganese slag leaching solution and bacterial solution; the manganese slag leaching solution contains divalent manganese, and the bacterial solution contains Klebsiella.

[0009] S2. Mix calcium acetate and the bacterial solution into the manganese slag leaching solution to obtain a culture solution; culture the culture solution for at least 30 h to obtain a reaction solution.

[0010] S3. Perform solid-liquid separation on the reaction solution to obtain a manganese-removed separation solution.

[0011] Further, the method for obtaining the manganese slag leaching solution includes: mixing electrolytic manganese slag and water at a mass ratio of 1:5 - 50, and then performing solid-liquid separation to obtain the manganese slag leaching solution.

[0012] Further, in the manganese slag leaching solution, the content of divalent manganese is 1000 - 1600 mg / L.

[0013] Further, the method for obtaining the bacterial solution includes: culturing Klebsiella in a liquid medium until Klebsiella is in the logarithmic growth phase; the nutrients in the liquid medium include sodium acetate and yeast extract powder.

[0014] Further, Klebsiella in the bacterial solution is in the logarithmic growth phase, and the volume percentage of the bacterial solution and the culture solution is not less than 4%.

[0015] Further, the concentration of calcium acetate in the culture solution is not less than 6 g / L.

[0016] Further, the initial pH of the culture solution is 7 - 9, and the culture temperature of the culture solution is 25 - 40 °C.

[0017] Further, the culture duration of the culture solution is 48 - 72 h.

[0018] The present invention also provides a method for culturing Klebsiella, including: adding Klebsiella-containing into a liquid medium and culturing; the nutrients in the liquid medium include sodium acetate and yeast extract powder.

[0019] Further, in the liquid medium, the concentration of sodium acetate is 10 - 30 g / L, the concentration of yeast extract powder is 2 - 6 g / L; the pH of the liquid medium is 7 - 9.

[0020] Compared with the prior art, the present invention has at least the following advantages:

[0021] The present invention can efficiently solidify divalent manganese in the manganese slag leaching solution based on microorganisms; specifically, by combining Klebsiella and calcium acetate, the present invention can effectively improve the solidification effect of Mn(II) in the electrolytic manganese slag leaching solution, greatly improve the treatment efficiency, and almost achieve the complete removal of Mn(II), that is, the combination of Klebsiella and calcium acetate can efficiently solidify Mn(II) in the electrolytic manganese slag leaching solution.

[0022] In specific applications, the present invention can be applied to treating divalent manganese leaching solution in manganese slag soil, and has the advantages of wide strain sources, low usage cost, environmental friendliness, no secondary pollution, etc.; since the present invention can efficiently solidify Mn(II) in manganese slag leaching solution in a short time and can be applied on a large scale, it has broad application prospects in the field of solidifying heavy metals by microbial methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for describing the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on the structures shown in these drawings.

[0024] Figure 1 It is the growth diagram of Klebsiella corresponding to different nutrients in Embodiment 1 of the present invention;

[0025] Figure 2 It is the growth diagram of Klebsiella corresponding to different initial pH values in Embodiment 2 of the present invention;

[0026] Figure 3 It is the growth diagram of Klebsiella corresponding to different culture temperatures in Embodiment 3 of the present invention;

[0027] Figure 4 It is the dot line diagram of the Mn(II) content in the filtrate corresponding to different initial pH values in Embodiment 4 of the present invention; in the figure, 0h refers to: the Mn(II) content in the electrolytic manganese slag leaching solution; other moments refer to: the Mn(II) content in the filtrate after filtration and separation of the culture solution at the corresponding culture time.

[0028] Figure 5 It is the dot line diagram of the Mn(II) content in the filtrate corresponding to different inoculation amounts of bacterial liquid in Embodiment 5 of the present invention; in the figure, 0h refers to: the Mn(II) content in the electrolytic manganese slag leaching solution; other moments refer to: the Mn(II) content in the filtrate after filtration and separation of the culture solution at the corresponding culture time.

[0029] Figure 6 It is the dot line diagram of the Mn(II) content in the filtrate corresponding to different dosages of calcium acetate added in Embodiment 6 of the present invention; in the figure, 0h refers to: the Mn(II) content in the electrolytic manganese slag leaching solution; other moments refer to: the Mn(II) content in the filtrate after filtration and separation of the culture solution at the corresponding culture time.

[0030] Figure 7SEM images of the morphology of Klebsiella before and after cultivation in the experimental group in Example 7 of the present invention; among them, (a) is Klebsiella before cultivation, and (b) is Klebsiella in the experimental group after 48 h of cultivation;

[0031] Figure 8 Bar chart of metal ion contents in the control group, the comparison group and the experimental group after cultivation in Example 7 of the present invention; in the figure, Mn refers to divalent manganese, Control group is the control group, 10% Kleb.sp is the comparison group, and 10%s Kleb.sp + 10 g / L CaAc is the experimental group.

[0032] The realization, functional features and advantages of the object of the present invention will be further described in conjunction with the embodiments with reference to the accompanying drawings. Detailed Embodiments

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0034] Moreover, the technical solutions between the various embodiments of the present invention can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement them. When the combination of technical solutions appears to be contradictory or unable to be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0035] When the embodiments give a numerical range, it should be understood that unless otherwise stated in the present invention, any value at both ends of each numerical range and any value between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention, based on the understanding of those of ordinary skill in the art of the prior art and the description of the present invention, can also use any method, device and material of the prior art similar or equivalent to the methods, devices and materials described in the embodiments of the present invention to implement the present invention.

[0036] In the embodiments of the present invention, the electrolytic manganese residue leaching solution (manganese residue leaching solution) is obtained by: after leaching (mixing) the ground electrolytic manganese residue and water in a mass ratio of 1:10, solid-liquid separation (filtration) is performed to obtain it; specifically, 10 g of the electrolytic manganese residue after drying and grinding through a 200-mesh sieve is mixed with 100 mL of deionized water and filtered to obtain the electrolytic manganese residue leaching solution. It should be noted that since the electrolytic manganese residue leaching solution is derived from the electrolytic manganese residue, there will still be some other elements and substances in the electrolytic manganese residue leaching solution; and since it is impossible to directly obtain a pure solution after filtration, in addition to divalent manganese, there will still be some manganese in a fixed form in the electrolytic manganese residue leaching solution. Therefore, in the present invention, since the electrolytic manganese residue leaching solution is derived from the electrolytic manganese residue, the electrolytic manganese residue leaching solution refers to its containing divalent manganese ions and cannot be absolutely understood as a pure solution without other substances and particulate matter.

[0037] In the embodiments of the present invention, the pH value is adjusted with 1M sulfuric acid and 1M sodium hydroxide solution; in the present invention, OD600 = 1 to 1.2 represents that the microorganisms in the bacterial solution reach the logarithmic growth phase. The Klebsiella in the present invention, named Klebsiella T-1, is a Gram-negative bacterium, belonging to the phylum Proteobacteria, family Enterobacteriaceae, genus Enterobacter, and is purchased from the China Center for Industrial Culture Collection, with the strain number CICC 10702. In the present invention, the substances and equipment used in contact with microorganisms are all sterilized or disinfected; in the present invention, the culture medium is prepared using deionized water as a solvent.

[0038] The present invention provides a method for efficiently solidifying manganese in manganese residue leaching solution based on microorganisms, including the steps:

[0039] S1, obtaining a manganese residue leaching solution and a bacterial solution; the manganese residue leaching solution contains divalent manganese; the bacterial solution contains Klebsiella.

[0040] The obtaining method of the manganese residue leaching solution includes: mixing the electrolytic manganese residue and water in a mass ratio of 1:5 to 50, and then performing solid-liquid separation to obtain the manganese residue leaching solution. For example: 10 g of the freshly dried and ground electrolytic manganese residue after passing through a 200-mesh sieve is mixed with 100 mL of deionized water and filtered to obtain the manganese residue leaching solution.

[0041] The manganese residue leaching solution has manganese ions, and the existing form of manganese ions in the manganese residue leaching solution includes divalent manganese; in the manganese residue leaching solution, the content of divalent manganese is 1000 to 1600 mg / L; further, in the manganese residue leaching solution, the content of divalent manganese is 1300 to 1600 mg / L.

[0042] The method for obtaining the bacterial liquid includes: placing the Klebsiella in a liquid medium and culturing it in an aerobic environment until the Klebsiella is in the logarithmic growth phase; the nutrients in the liquid medium include sodium acetate and yeast extract powder; the concentration of sodium acetate in the liquid medium is 10-30 g / L, the concentration of yeast extract powder is 2-6 g / L, and the pH of the liquid medium is 7-9; the liquid medium may also contain tryptone and sodium chloride, the concentration of tryptone can be 8-12 g / L, and the concentration of sodium chloride can be 8-10 g / L.

[0043] S2. Mix calcium acetate and the bacterial liquid into the manganese slag leaching solution to obtain a culture solution; culture the culture solution for at least 30 h to obtain a reaction solution.

[0044] In the present invention, the concentration of calcium acetate in the culture solution is not less than 6 g / L. Further, the concentration of calcium acetate in the culture solution is 6-10 g / L or 6-8 g / L or 8-10 g / L. In the present invention, the Klebsiella in the bacterial liquid is in the logarithmic growth phase, and the volume percentage of the bacterial liquid and the culture solution is not less than 4%; further, the volume percentage of the bacterial liquid and the culture solution is 6-12% or 6-10% or 8-10%.

[0045] In the present invention, the culturing is carried out in an aerobic environment; in the present invention, nutrients for the growth of Klebsiella can be selectively added to the culture solution according to actual conditions. In the present invention, the initial pH of the culture solution is 7-9, the culturing temperature of the culture solution is 25-40 °C, further 30-35 °C. In the present invention, the culturing duration of the culture solution is further 48-72 h or 60-72 h or 70-72 h.

[0046] S3. Perform solid-liquid separation on the reaction solution to obtain a manganese-removed separation liquid and a manganese-containing tailing slag.

[0047] Under the induction condition of calcium acetate in the present invention, Mn(II) in the leaching solution is promoted to mineralize and solidify, so as to achieve the purpose of efficiently removing Mn(II) in the manganese slag leaching solution.

[0048] The present invention provides a method for culturing Klebsiella, including: adding Klebsiella-containing to a liquid medium and culturing it; the culturing is carried out in an aerobic environment. The nutrients in the liquid medium include sodium acetate and yeast extract powder; the concentration of sodium acetate in the liquid medium is 10-30 g / L, the concentration of yeast extract powder is 2-6 g / L, and the pH of the liquid medium is 7-9. The liquid medium may also contain tryptone and sodium chloride, the concentration of tryptone can be 8-12 g / L, and the concentration of sodium chloride can be 8-10 g / L.

[0049] The following are specific examples of the present invention:

[0050] Example 1

[0051] This example explores the effects of different nutrients on the growth of Klebsiella, and the specific steps are as follows:

[0052] Step 1: Incorporate the bacterial agent of Klebsiella into the enrichment solution, mix well and shake to obtain an enrichment bacterial solution with a concentration of 4%; the components of the enrichment solution are 80 g / L sodium acetate and 4 g / L yeast extract powder, and the pH of the enrichment solution is 7.

[0053] Step 2: Add 5 mL of the enrichment bacterial solution to 250 mL of the liquid medium, and culture it in an aerobic environment for 60 h, and perform detection at regular intervals; the initial pH of the liquid medium is 7; the culture temperature is 30 °C; the rotation speed during the culture process is 100 rpm.

[0054] In this example, the nutrients in the liquid medium are respectively: 4 g / L yeast extract powder (YE), 20 g / L sodium acetate (NaAc), 4 g / L yeast extract powder + 20 g / L sodium acetate (YE + NaAc), 2 g / L urea (Urea), 4 g / L yeast extract powder + 2 g / L urea (Urea + YE); culture is carried out respectively under the conditions of the above-mentioned various nutrients. The other components in the liquid medium are: 10 g / L tryptone and 10 g / L sodium chloride.

[0055] Step 3: Use a spectrophotometer to measure the OD600 value of the bacterial solution corresponding to the liquid medium during culture, analyze the growth rate of Klebsiella, and record the differences in the growth and reproduction of Klebsiella among different control groups.

[0056] See Figure 1 As shown, the order of the growth rates corresponding to different nutrients is: sodium acetate + yeast > yeast > urea + yeast > sodium acetate > urea, that is, when the nutrient is a combination of sodium acetate + yeast, the culture effect of Klebsiella is excellent.

[0057] Example 2

[0058] This example explores the effects of different initial pH values on the growth of Klebsiella, and the specific steps are as follows:

[0059] Step 1: Incorporate the bacterial agent of Klebsiella into the enrichment solution, mix well and shake to obtain an enrichment bacterial solution with a concentration of 4%; the components of the enrichment solution are 80 g / L sodium acetate and 4 g / L yeast extract powder, and the pH of the enrichment solution is 7.

[0060] Step 2: Add 5 mL of the enriched bacterial solution to 250 mL of the liquid medium, and culture it in an aerobic environment for 60 h, with regular detection; the composition of the liquid medium is 20 g / L sodium acetate, 4 g / L yeast extract powder, 10 g / L tryptone, and 10 g / L sodium chloride; the culture temperature is 30 °C; the rotation speed during the culture process is 100 rpm.

[0061] In this example, while keeping other conditions the same, the initial pH values of the liquid medium are 5, 6, 7, 8, and 9 respectively; culture is carried out under the conditions of the above respective initial pH values.

[0062] Step 3: Use a spectrophotometer to measure the OD600 value of the bacterial solution corresponding to the liquid medium during culture, analyze the growth rate of Klebsiella, and record the differences in the growth and reproduction of Klebsiella among different control groups.

[0063] See Figure 2 As shown, the order of the growth rates corresponding to different pH values is: neutral or slightly alkaline (pH 7, pH 8, pH 9) > slightly acidic (pH 5, pH 6), that is, when the system pH is neutral or slightly alkaline, the culture effect of Klebsiella is excellent.

[0064] Example 3

[0065] This example explores the influence of the culture temperature on the growth of Klebsiella, and the specific steps are as follows:

[0066] Step 1: Incorporate the bacterial agent of Klebsiella into the enrichment solution, mix and shake well to obtain an enriched bacterial solution with a concentration of 4%; the composition of the enrichment solution is 80 g / L sodium acetate and 4 g / L yeast extract powder, and the pH of the enrichment solution is 7.

[0067] Step 2: Add 5 mL of the enriched bacterial solution to 250 mL of the liquid medium, and culture it in an aerobic environment for 60 h, with regular detection; the composition of the liquid medium is 20 g / L sodium acetate, 4 g / L yeast extract powder, 10 g / L tryptone, and 10 g / L sodium chloride; the initial pH of the liquid medium is 7; the rotation speed during the culture process is 100 rpm.

[0068] In this example, while keeping other conditions the same, the culture temperatures are 25 °C, 30 °C, 35 °C, and 40 °C respectively; culture is carried out under the conditions of the above respective culture temperatures.

[0069] Step 3: Use a spectrophotometer to measure the OD600 value of the bacterial solution corresponding to the liquid medium during culture, analyze the growth rate of Klebsiella, and record the differences in the growth and reproduction of Klebsiella among different control groups.

[0070] See Figure 3As shown, the growth rate corresponding to different culture temperatures is ranked as: 30°C > 35°C > 25°C > 40°C, that is, when the culture temperature is 30°C, the culture effect of Klebsiella is excellent.

[0071] Example 4

[0072] This example explores the effect of different pH values on Mn(II) in the leaching solution of solidified electrolytic manganese slag by Klebsiella, and the specific steps are as follows:

[0073] Step 1: Place Klebsiella in a liquid medium and culture it in an aerobic environment until the logarithmic growth phase to obtain a bacterial solution; the components of the liquid medium are 20 g / L sodium acetate, 4 g / L yeast extract, 10 g / L tryptone, and 10 g / L sodium chloride; the initial pH of the liquid medium is 7; the culture temperature is 30°C; the rotation speed during the culture process is 100 rpm.

[0074] Step 2: Add calcium acetate and the above bacterial solution to the electrolytic manganese slag leaching solution to obtain a culture solution, and culture the culture solution in an aerobic environment for 72 h; take out the culture solution regularly, filter it, and detect the content of Mn(II) in the filtrate with an inductively coupled plasma emission spectrometer.

[0075] In this example, the volume percentage (inoculation amount) of the bacterial solution and the culture solution is 10%; the concentration of calcium acetate in the culture solution is 8 g / L (calcium acetate dosage); the culture temperature is 30°C, and the rotation speed during the culture process is 100 rpm; in the electrolytic manganese slag leaching solution, the concentration of divalent manganese ions is 1472 mg / L.

[0076] In this example, while keeping other conditions the same, the initial pH values of the culture solution are 5, 6, 7, 8, and 9 respectively.

[0077] See Figure 4 As shown, under the conditions of initial pH = 7, 8, and 9, the content of Mn(II) all reaches below 5 mg / L; considering cost and environmental factors, that is, when the pH value of the reaction system is 7, the efficiency of fixing manganese slag leaching solution (II) is excellent. In addition, under the condition of initial pH = 5, due to the acidic environment, some fixed forms of manganese dissolve to form divalent manganese ions, resulting in an increase in the concentration of divalent manganese ions.

[0078] Specifically, in this example, when the initial pH is 7, the content of Mn(II) in the filtrate is 5.76 mg / L when cultured for 50 h; when the initial pH is 7, the content of Mn(II) in the filtrate is 3.49 mg / L when cultured for 72 h.

[0079] Example 5

[0080] This example explores the effect of different inoculation amounts of bacterial solution on Mn(II) in the leaching solution of solidified electrolytic manganese residue by Klebsiella, and the specific steps are as follows:

[0081] Step 1: Place Klebsiella in a liquid medium and culture it in an aerobic environment until the logarithmic growth phase to obtain a bacterial solution; the components of the liquid medium are 20 g / L sodium acetate, 4 g / L yeast extract powder, 10 g / L tryptone, and 10 g / L sodium chloride; the initial pH of the liquid medium is 7; the culture temperature is 30 °C; the rotation speed during the culture process is 100 rpm.

[0082] Step 2: Add calcium acetate and the above-mentioned bacterial solution to the electrolytic manganese residue leaching solution to obtain a culture solution, and culture the culture solution in an aerobic environment for 72 h; take out the culture solution regularly, filter it, and detect the Mn(II) content in the filtrate with an inductively coupled plasma emission spectrometer.

[0083] In this example, the initial pH of the culture solution is 7; the concentration of calcium acetate in the culture solution is 8 g / L (calcium acetate dosage); the culture temperature is 30 °C, and the rotation speed during the culture process is 100 rpm; in the electrolytic manganese residue leaching solution, the concentration of divalent manganese ions is 1542 mg / L.

[0084] In this example, the volume percentages (inoculation amounts) of the bacterial solution and the culture solution are 0%, 4%, 6%, 8%, and 10% respectively; 0% represents no addition of the bacterial solution (No bacterium).

[0085] See Figure 5 As shown, after 72 h of culture (microbial solidification reaction), a higher proportion of the bacterial solution can effectively reduce the free Mn(II) in the manganese residue leaching system, and it basically reaches equilibrium after 60 h of reaction. The removal efficiency of Mn(II) in the groups with bacteria is all above 99.5%; as the reaction time prolongs, the removal rates of each group with bacteria are basically the same, and the initial concentration of microorganisms is the key factor affecting the reaction rate; when the inoculation amount of the bacterial solution is 10%, the rate of fixing Mn(II) in the electrolytic manganese residue leaching solution is excellent.

[0086] Specifically, in this example, when the inoculation amount of the bacterial solution is 10%, the content of Mn(II) in the filtrate is 4.44 mg / L at 60 h of culture; the content of Mn(II) in the filtrate is 3.62 mg / L at 72 h of culture.

[0087] Example 6

[0088] This example explores the effect of different calcium acetate dosages on Mn(II) in the leaching solution of solidified electrolytic manganese residue by Klebsiella, and the specific steps are as follows:

[0089] Step 1: Place Klebsiella in a liquid medium and culture it in an aerobic environment until the logarithmic growth phase to obtain a bacterial solution; the composition of the liquid medium is 20 g / L sodium acetate, 4 g / L yeast extract powder, 10 g / L tryptone, and 10 g / L sodium chloride; the initial pH of the liquid medium is 7; the culture temperature is 30 °C; the rotation speed during the culture process is 100 rpm.

[0090] Step 2: Add calcium acetate and the above-mentioned bacterial solution to the electrolytic manganese slag leaching solution to obtain a culture solution, and culture the culture solution in an aerobic environment for 72 h; regularly take out the culture solution, filter it, and detect the Mn(II) content in the filtrate using an inductively coupled plasma emission spectrometer.

[0091] In this example, the volume percentage (inoculation amount) of the bacterial solution and the culture solution is 10%, the initial pH of the culture solution is 7; the culture temperature is 30 °C, and the rotation speed during the culture process is 100 rpm; in the electrolytic manganese slag leaching solution, the concentration of divalent manganese ions is 1508 mg / L.

[0092] In this example, the concentrations of calcium acetate in the culture solution are 0 g / L, 2 g / L, 4 g / L, 6 g / L, and 8 g / L (calcium acetate dosage); 0 g / L represents no calcium acetate added (Blank).

[0093] See Figure 6 As shown, after a 72-hour microbial solidification reaction, when the calcium acetate dosage reaches 8 g / L, the Mn(II) removal rate is the highest; when calcium acetate is lacking in the system, the concentration of Mn(II) in the filtrate shows a significant decrease, and calcium acetate is a necessary condition for the continuous progress of the whole process; that is, when the calcium acetate dosage reaches 8 g / L, the Mn(II) removal rate of the fixed manganese slag leaching solution is excellent.

[0094] Example 7

[0095] This example explores the method for solidifying the electrolytic manganese slag leaching solution under the comprehensive optimal conditions of Klebsiella, including the following steps:

[0096] Step 1: Place Klebsiella in a liquid medium and culture it in an aerobic environment until the logarithmic growth phase to obtain a bacterial solution; the composition of the liquid medium is 20 g / L sodium acetate, 4 g / L yeast extract powder, 10 g / L tryptone, and 10 g / L sodium chloride; the initial pH of the liquid medium is 7; the culture temperature is 30 °C; the rotation speed during the culture process is 100 rpm.

[0097] Step 2:

[0098] (1) Control group: Take the electrolytic manganese slag leaching solution as the control group; in the electrolytic manganese slag leaching solution, the concentration of divalent manganese ions is 1498.21 mg / L.

[0099] (2) Control group: Add the bacterial solution obtained in step 1 into the electrolytic manganese residue leaching solution to obtain a culture solution, and culture the culture solution for 48 h; the volume percentage of the bacterial solution and the culture solution is 10%, and the initial pH of the culture solution is 7; the culture temperature is 30 °C, and the rotation speed during the culture process is 100 rpm; in the electrolytic manganese residue leaching solution, the concentration of divalent manganese ions is 1501.13 mg / L.

[0100] (3) Experimental group: Add calcium acetate and the bacterial solution obtained in step 1 into the electrolytic manganese residue leaching solution to obtain a culture solution, and culture the culture solution for 48 h; the volume percentage of the bacterial solution and the culture solution is 10%, and the initial pH of the culture solution is 7; the concentration of calcium acetate in the culture solution is 8 g / L; the culture temperature is 30 °C, and the rotation speed during the culture process is 100 rpm; in the electrolytic manganese residue leaching solution, the concentration of divalent manganese ions is 1508.26 mg / L.

[0101] See Figure 7 As shown, observe the morphology of the strains in the experimental group before and after 48 h of culture. It can be seen that: the overall morphology of Klebsiella has not been damaged, and it still presents a complete cell morphology, but the cell surface becomes wrinkled after the reaction.

[0102] See Figure 8 As shown, after filtration, use an inductively coupled plasma emission spectrometer to detect the metal ion content in the filtrate; it can be seen that: in the experimental group, the dissolution of Mn(II) is significantly improved, and the Mn(II) concentration is reduced from 1508.26 mg / L to 2.67 mg / L. The solidification rate of Klebsiella strains for Mn(II) can reach more than 99.8%, that is, the combination of Klebsiella and calcium acetate can efficiently solidify Mn(II) in the electrolytic manganese residue leaching solution.

[0103] In the above technical solution of the present invention, the above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention. Any equivalent structural transformation made under the technical concept of the present invention by using the content of the specification and drawings of the present invention, or directly / indirectly applied in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A method for efficiently solidifying manganese in the leaching solution of manganese slag based on microorganisms, characterized in that, Including the steps: S1. Obtain a manganese slag leaching solution and a bacterial solution; the manganese slag leaching solution contains divalent manganese, and the bacterial solution contains Klebsiella; The method for obtaining the manganese slag leaching solution includes: mixing electrolytic manganese slag and water in a mass ratio of 1:5 to 50, and then performing solid-liquid separation to obtain the manganese slag leaching solution; S2. Mix calcium acetate and the bacterial solution into the manganese slag leaching solution to obtain a culture solution; culture the culture solution for at least 30 h to obtain a reaction solution; S3. Perform solid-liquid separation on the reaction solution to obtain a manganese-removed separation solution.

2. The method for efficiently solidifying manganese in a manganese slag leaching solution based on microorganisms according to claim 1, wherein the content of divalent manganese in the manganese slag leaching solution is 1000-1600 mg / L.

3. The method for efficiently solidifying manganese in the leaching solution of manganese slag based on microorganisms according to claim 1 is characterized in that, The method for obtaining the bacterial solution includes: culturing the Klebsiella in a liquid medium until the Klebsiella is in the logarithmic growth phase; the nutrients in the liquid medium include sodium acetate and yeast extract powder.

4. The method for efficiently solidifying manganese in a manganese slag leaching solution based on microorganisms according to claim 1, wherein the Klebsiella in the bacterial solution is in the logarithmic growth phase, and the volume percentage of the bacterial solution and the culture solution is not less than 4%.

5. The method for efficiently solidifying manganese in a manganese slag leaching solution based on microorganisms according to claim 1, wherein the concentration of calcium acetate in the culture solution is not less than 6 g / L.

6. The method for efficiently solidifying manganese in a manganese slag leaching solution based on microorganisms according to claim 1, wherein the initial pH of the culture solution is 7-9, and the culture temperature of the culture solution is 25-40 °C.

7. The method for efficiently solidifying manganese in a manganese slag leaching solution based on microorganisms according to claim 1, wherein the culture duration of the culture solution is 48-72 h.

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