Method for synthesizing ca2al3o6f by mineralizing phosphogypsum with gluconobacter cerinus

Abstract

The application discloses a method for synthesizing Ca2Al3O6F by mineralizing phosphogypsum with gluconacetobacter cerinus, and belongs to the fields of phosphogypsum resource utilization and Ca2Al3O6F mineral synthesis. The method comprises the following steps: culturing the gluconacetobacter cerinus in a culture medium containing phosphogypsum, wherein the particle size of the phosphogypsum is 50-200 meshes, and the content of the phosphogypsum is 4-10 g / L; and the culture medium comprises 20 g / L of trypsin, 10 g / L of yeast extract and 20 g / L of glucose, and the pH value is 4-7. After the gluconacetobacter cerinus is cultured in the culture medium containing the phosphogypsum, the synthesized Ca2Al3O6F is enriched on the surface of the gluconacetobacter cerinus. The application not only realizes the harmless treatment of the phosphogypsum, but also realizes the synthesis of the Ca2Al3O6F mineral by using the biological method to replace the chemical method. The application integrates the phosphogypsum resource utilization and the Ca2Al3O6F mineral utilization, and can obtain good economic benefits and social benefits.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of phosphogypsum resource utilization and Ca2Al3O6F mineral synthesis, and particularly relates to a method for synthesizing Ca2Al3O6F from wax-like gluconobacter mineralized phosphogypsum. BACKGROUND

[0002] Oxyfluoride-embedded rare earth ions are an important source for synthesizing new compounds with unique luminescent properties. Ca2Al3O6F :Eu 2+ is a green-emitting oxyfluoride phosphor (Xia Zhiguo et al., Ca2Al3O6F :Eu 2 + : a green-emitting oxyfluoride phosphor for white light-emitting diodes, J. Mater. Chem., 2012, 22, 15183-15189), and Ca2Al3O6F :Ce 3+ ,Tb 3+ is a phosphor that can tune blue-green light emission and energy transfer (Xia Zhiguo et al., Tunable Blue-green color emission and energy transfer of Ca2Al3O6F :Ce 3+ ,Tb 3+ phosphors for near-UV white LEDs, J. Phys. Chem., C 2012, 116, 15604-15609), and can be used in display screens, fluorescent lamps, ionizing radiation detection, aircraft instrument panels, lasers, and infrared night vision devices. Therefore, Ca2Al3O6F (calcium aluminum oxyfluorite) is a mineral material with important application prospects and has potential application value in the field of phosphor materials. The synthesis of the mineral mainly uses chemical methods such as solid-phase reaction, sol-gel method, and molten salt method. There is no report on the synthesis of the mineral by a biological method.

[0003] Phosphogypsum is a solid waste residue produced in the production process of wet-process phosphoric acid, and in addition to containing calcium sulfate dihydrate (CaSO4·2H2O), it also contains elements such as phosphorus, silicon, iron, aluminum, sulfur, and fluorine. The waste residue is rich in all elements for synthesizing Ca2Al3O6F minerals.

[0004] It has been reported that the use of microbially induced carbonate precipitation (MICP) technology can remove impurities and heavy metal ions in phosphogypsum, such as the use of Bacillus pasteurianus to induce mineralization of phosphogypsum and sand fixation. Gluconobacter cerinus ) is a Gram-negative bacterium found widely in nature, such as on fruit skin and in soil. Gluconobacter cereus can be used to produce 2-keto-L-gulonic acid, a key precursor for vitamin C synthesis. Gluconobacter cereus possesses a robust metabolic capacity, capable of incompletely oxidizing a variety of sugars under aerobic conditions to produce the corresponding ketose or aldonic acids. This unique metabolic property provides a foundation for its application in environmental bioremediation, including its potential for adsorption of heavy metals (such as lead and cadmium) in the environment. However, whether this bacterium can be used to synthesize the mineral Ca2Al3O6F has not been reported. Summary of the Invention

[0005] The present invention found that Gluconobacter cereus ( Gluconobacter cerinus ) is a bioleaching strain that leaches phosphogypsum, removing harmful substances while simultaneously producing Ca2Al3O6F minerals. Based on this, the present invention aims to provide a method for mineralizing phosphogypsum with Gluconobacter cereus to synthesize Ca2Al3O6F. This method not only achieves harmless treatment of phosphogypsum but also utilizes biological methods to replace chemical methods for synthesizing Ca2Al3O6F minerals.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A method for synthesizing Ca2Al3O6F by mineralizing phosphogypsum with Gluconobacter cereus comprises culturing Gluconobacter cereus in a culture medium containing phosphogypsum, and enriching the synthesized Ca2Al3O6F on the surface of Gluconobacter cereus.

[0008] In some preferred embodiments, the Gluconobacter cereus is Gluconobacter cereus with a deposit number of GDMCC No: 66080 ( Gluconobacter cerinus ) VDK-N. The deposit information of Gluconobacter cereus VDK-N is as follows: Depository: Guangdong Microbial Culture Collection Center (GDMCC), Deposit Address: 5th Floor, Building 59, No. 100 Xianlie Middle Road, Guangzhou, Institute of Microbiology, Guangdong Academy of Sciences, Deposit Date: March 31, 2025, Deposit Number: GDMCC No: 66080, Classification Name: Gluconobacter cerinus .

[0009] In some preferred embodiments, the culture medium comprises: 15-25 g / L of tryptone, 5-15 g / L of yeast extract, 15-25 g / L of glucose, and has a pH of 4-7. Further preferably, the culture medium comprises: 20 g / L of tryptone, 10 g / L of yeast extract, and 20 g / L of glucose.

[0010] In some preferred embodiments, the phosphogypsum is phosphogypsum powder with a particle size of 50-200 mesh; and the content of the phosphogypsum is 4-10 g / L.

[0011] In some preferred embodiments, the culture condition is 25-35℃ for 5-10 days. Further preferably, the culture is shaking culture, and the rotation speed is preferably 150-180 r / min.

[0012] Further, the method for synthesizing Ca2Al3O6F by using the mineralized phosphogypsum of the Gluconacetobacter cerinus comprises the following steps: inoculating the Gluconacetobacter cerinus in logarithmic growth phase into a culture medium containing phosphogypsum for shaking culture. Preferably, the inoculation amount of the Gluconacetobacter cerinus is 5-20% (v / v).

[0013] The present application has the following advantages and beneficial effects:

[0014] The method for synthesizing Ca2Al3O6F mineral by using the biological method of the present application is simple in operation and good in synthesis effect. This not only solves the fluorine pollution problem of the phosphogypsum, but also provides an environment-friendly method for synthesizing Ca2Al3O6F mineral, thereby laying a foundation for the application of Ca2Al3O6F mineral.

[0015] The present application integrates the resource utilization of phosphogypsum and the utilization of Ca2Al3O6F mineral, and can obtain good economic benefits and social benefits. Therefore, the present application has a broad development prospect. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 It is an original electron microscope morphology diagram of the Gluconacetobacter cerinus.

[0017] Figure 2 It is an electron microscope diagram of the Gluconacetobacter cerinus after mineralizing the phosphogypsum.

[0018] Figure 3 It is an electron microscope diagram of the original morphology of the phosphogypsum.

[0019] Figure 4 It is an electron microscope diagram of the phosphogypsum after being treated by the Gluconacetobacter cerinus.

[0020] Figure 5 It is an XRD crystal structure characterization result of the mineralized crystal on the surface of the Gluconacetobacter cerinus. DETAILED DESCRIPTION

[0021] In order to more clearly illustrate the technical solutions and technical effects of the present application, the specific embodiments of the present application will be described in detail below. Obviously, for those skilled in the art, other embodiments can also be obtained from these embodiments without creative effort. It should be understood that the embodiments described herein are only used to explain the present application and not to limit the present application.

[0022] The strains and reagents used in the following examples are as follows:

[0023] Gluconacetobacter cerinus VDK-N: Fresh vineyard soil was collected from Shalinqin Town, Donghe District, Baotou City, Inner Mongolia. 5 g of soil was added to 45 mL of ddHO, and the soil mixture was vigorously shaken in a constant temperature shaker for 15 minutes to ensure that the microorganisms in it were completely suspended in the supernatant. The supernatant was selected to enrich the strains in the soil. YPD medium was used for isolation and purification, and the strain was obtained. The preservation information of Gluconacetobacter cerinus VDK-N is as follows: preservation unit: Guangdong Microbial Culture Collection Center (GDMCC), preservation address: 5th floor, No. 59 Building, Institute of Microbiology, Guangdong Academy of Sciences, 100 Middle Martyrs Road, Guangzhou, preservation date: March 31, 2025, preservation number: GDMCC No: 66080, classification and naming: Gluconobacter cerinus .

[0024] Phosphogypsum: from Hubei Yidu Xingfa Chemical Co., Ltd.

[0025] Tryptone: purchased from Shanghai Genechem Co., Ltd.

[0026] Yeast extract: purchased from OXOID Company.

[0027] Glucose: purchased from Shanghai McLean Biochemical Science and Technology Co., Ltd.

[0028] Example 1

[0029] This embodiment provides a method for synthesizing Ca2Al3O6F mineral by mineralizing phosphogypsum by Gluconacetobacter cerinus, which specifically comprises the following steps: Gluconobacter cerinus

[0030] (1) Preparation of phosphogypsum powder:

[0031] The phosphogypsum was first passed through a 140-mesh sieve, and then the filtered phosphogypsum was passed through a 170-mesh sieve for standby use.

[0032] (2) Preparation of Ca2Al3O6F mineral synthesis medium:

[0033] ​The YPD culture medium is prepared by using YPD culture medium components and phosphogypsum powder, and the YPD culture medium components include 20 g / L of tryptone, 10 g / L of yeast extract, 20 g / L of glucose and 10 g / L of phosphogypsum powder, and the pH is 6.81.

[0034] (3) The log growth phase of the C. cereus is inoculated into the mineral synthetic culture medium at a 10% inoculation amount, and then cultured at 150-180 r / min and 30°C in a shaking bed for 10 days.

[0035] The morphological changes of the C. cereus before and after the mineralization of the phosphogypsum, and the morphological changes of the phosphogypsum before and after the treatment are observed by using an electron microscope. Figure 1 、 2 As shown in the electron microscope images of the C. cereus before and after the mineralization of the phosphogypsum, Figure 1 , the original strain has a spherical or rod-like shape, the two ends are flat, the surface is smooth, and the bacteria exist independently. Figure 2 After the C. cereus is cultured in the culture medium containing the phosphogypsum, mineralized crystals are formed on the surface of the bacteria. Figure 3 、 4 As shown in the electron microscope images of the phosphogypsum before and after the treatment, Figure 3 , the surface of the phosphogypsum before the treatment is not smooth, and has rich attachments, which contain soluble fluorine and soluble organic matter. Figure 4 The surface of the phosphogypsum after the treatment is smooth and uniform.

[0036] The mineralized crystals on the surface of the C. cereus are characterized by XRD, and the results are shown in Figure 5 The first large peak in the figure is the original component CaSO4 of the phosphogypsum, and the second large peak is the synthesized mineral Ca2Al3O6F, which indicates that the C. cereus synthesizes Ca2Al3O6F. The EDS energy spectrum analysis of the phosphogypsum before and after the treatment shows that the phosphogypsum before the treatment contains C, N, O, F, Al, Si, S, Ca and other elements, and the phosphogypsum after the treatment contains C, N, O, Al, Si, S, Ca, and fluorine element is not detected.

[0037] Example 2

[0038] According to the method in Example 1, phosphogypsum with particle size of 50-100 mesh is selected, a Ca2Al3O6F mineral synthesis medium is prepared, the pH of the medium is adjusted to 6.0, the gluconobacter cerinus in logarithmic growth phase is inoculated into the mineral synthesis medium, and the culture is shaken and cultured at 30°C for 10 days. Microscopy and XRD analysis are performed on the mineral synthesis, and the results show that the Ca2Al3O6F is synthesized on the surface of the gluconobacter cerinus.

[0039] Example 3

[0040] According to the method in Example 1, phosphogypsum with particle size of 150-200 mesh is selected, a Ca2Al3O6F mineral synthesis medium is prepared, the concentration of the phosphogypsum is adjusted to 4 g / L, the pH of the medium is adjusted to 5.0, the gluconobacter cerinus in logarithmic growth phase is inoculated into the mineral synthesis medium, and the culture is shaken and cultured at 27°C for 10 days. Microscopy and XRD analysis are performed on the mineral synthesis, and the results show that the Ca2Al3O6F is synthesized on the surface of the gluconobacter cerinus.

[0041] The above examples are only used to illustrate the present application, and those skilled in the art can make other different forms of changes or variations on the basis of the above description. Other changes or variations derived from the above changes or variations still belong to the protection scope of the present application.

Claims

1. A method of producing calcium phosphate (CaP) comprising: culturing a strain of the species Gluconobacter cerinus (G. cerinus) in a culture medium comprising a source of phosphate ions and a source of calcium ions; and recovering the calcium phosphate from the culture medium. Gluconobacter cerinus A method of synthesizing Ca2Al3O6F from mineralized phosphogypsum, characterized in that: The method is culturing Gluconobacter cerinus by using a culture medium containing phosphogypsum.

2. The method of claim 1, wherein: The Gluconobacter cerinus has a preservation number of GDMCC No: 66080.

3. The method of claim 1, wherein, The culture medium contains 4-10 g / L of phosphogypsum, 15-25 g / L of tryptone, 5-15 g / L of yeast extract, 15-25 g / L of glucose, and has a pH of 4-7.

4. The method of claim 3, wherein, The culture medium contains 4-10 g / L of phosphogypsum, 20 g / L of tryptone, 10 g / L of yeast extract, and 20 g / L of glucose.

5. The method of claim 1, wherein: The phosphogypsum is phosphogypsum powder with a particle size of 50-200 mesh.

6. The method of claim 1, wherein: The culture condition is 25-35 DEG C for 5-10 days.

7. The method of claim 1, wherein: The culture is shaking culture with a rotation speed of 150-180 r / min.

8. The method of claim 1, wherein, The method comprises the following steps: logarithmic growth phase Gluconobacter cerinus is inoculated into a culture medium containing phosphogypsum for shaking culture.

9. The method of claim 8, wherein: The inoculation amount of the Gluconobacter cerinus is 5-20%.

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