Core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor, preparation method and application thereof

Abstract

The application discloses a kind of core-shell structure single-hole SiO2 hollow ball load microbial bioreactor and its preparation method and application, with SiO2 as base material, by the method of directional control, single-hole SiO2 hollow ball is prepared, load microorganism, as the part of core;Shell part uses silane hydrolysis to generate and contain SiO2 nanoparticles, and a core-shell structure bioreactor with selective adsorption and in-situ biodegradation is prepared.The core-shell structure bioreactor constructed by the application plays a key role in protecting microorganisms and preventing microorganism leakage as an independent closed specific space, the core-shell structure single-hole SiO2 hollow ball belongs to μm level, size is small, has low surface energy, large specific surface area to improve adsorption capacity, excellent oil-water separation capacity and emulsified oil demulsification capacity, and the material has good degradation characteristics to adsorbed oil by loading microorganism, and the material presents strong thermal stability and tolerance to surrounding adverse environment.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of material chemistry, and particularly relates to a core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor and a preparation method and application thereof. BACKGROUND

[0002] A large amount of oil-containing wastewater is generated in oil exploitation and processing, and the oil-containing wastewater is a huge industrial pollutant, which can produce various drug-resistant and toxic organic pollutants when discharged without treatment or partial treatment. At present, the treatment of oil-containing wastewater mainly aims at incompatible dispersed oil-containing wastewater, and with the development of industry, emulsifiers and surfactants are widely used, so that more and more oil-containing wastewater is in the state of emulsified oil. If the emulsified oil is directly discharged into the environment without treatment, it will pollute water resources, harm aquatic organisms, threaten human health, and cause irreversible damage to nature. However, the emulsified oil is difficult to separate because of its small size and mutual solubility with water, which makes many researchers hesitate, and the petroleum hydrocarbon pollutants will produce secondary pollution if not degraded in time. Therefore, effective oil-water separation and rapid degradation of emulsified oil have become a new research hotspot.

[0003] At present, the materials for oil-water separation in the treatment of oil-containing wastewater are mainly super-wetting porous materials such as sponge, membrane, aerogel and the like. For the floating oil or suspended oil in water, the application of the above super-wetting materials has been proved to be very effective, because they have strong affinity with oil and thus have high absorption selectivity, which has obvious advantages compared with traditional absorbents. However, in most cases, it is quite difficult to recover or treat the absorbed oil, which may cause the risk of secondary pollution. In addition, in the case of emulsified oil, the effect of these super-wetting materials is often unsatisfactory. In view of this problem, we first proposed a two-in-one technology in the previous study, that is, combining the selective absorption of oil or organic matter and biodegradation to remove and eliminate the oil in water at one step. This two-in-one strategy is more effective, because the absorbed oil does not need to be further treated and can be biodegraded. However, the challenge still exists, because the random loading of microorganisms into the pores or channels of the porous material cannot ensure the stable fixation of the microorganisms, which may lead to the risk of microorganism leakage. On the other hand, the super-wetting porous material loaded with biodegradable microorganisms does not have the ability to treat emulsified oil-containing wastewater.

[0004] In order to solve the above problems, it is of great significance to further explore the material which can not only stably fix microorganisms but also has high separation performance on emulsified oil. The application prepares a new type of microorganism reactor (M / Microbe@SHMs), which is based on fixing microorganisms in single-hole SiO2hollow spheres with core-shell structure and is used for selectively absorbing and biodegrading oil in water. The micro-sized biological reactor with super-hydrophobicity and super-oleophilic wettability can efficiently treat emulsified oil and has excellent selectivity and biodegradation performance. SUMMARY

[0005] The application aims to provide a preparation method of a hydrophobic and oleophilic green and environmentally friendly material with core-shell structure.

[0006] In order to achieve the above-mentioned purpose, the application provides the following technical scheme:

[0007] The preparation method of the core-shell structure single-hole SiO2hollow sphere loaded microorganism biological reactor comprises the following steps:

[0008] Step one: preparation of ternary phase (W / O / W) microemulsion

[0009] Step two: preparation of single-hole SiO2hollow sphere

[0010] Step three: culture of bacterial suspension

[0011] Step four: preparation of single-hole SiO2hollow sphere loaded microorganism biological reactor

[0012] Step five: preparation of nano-sized SiO2particles

[0013] Step six: preparation of single-hole SiO2hollow sphere loaded microorganism biological reactor with core-shell structure.

[0014] Preferably, the preparation of the ternary phase (W / O / W) microemulsion comprises:

[0015] (1) preparation of inner water phase (IWP): 36 mL of sodium silicate solution is mixed with 8 mL of sodium polyacrylate solution, and the sodium silicate is fully dissolved in the solution by stirring, and the liquid has no obvious particles;

[0016] (2) preparation of oil phase (OP): 36 mL of n-hexane, 0.75 g of Tween 80 and 0.75 g of Span 80 are fully mixed and uniformly mixed;

[0017] (3) preparation of outer water phase (OWP): first, 84 g of ammonium bicarbonate (NH4HCO3) is dissolved in 500 mL of distilled water to prepare a 2 mol / L ammonium bicarbonate aqueous solution, and 100 mL of 2 mol / L ammonium bicarbonate is taken as the outer water phase;

[0018] (4) ternary phase (W / O / W) preparation: first, OP is added to IWP and emulsified at 8000 rpm for 5 min, and then the mixed solution is added to OWP and stirred vigorously for 3 h, at which time a white emulsion-like viscous liquid is formed;

[0019] Preferably, the preparation of the single-hole SiO2hollow spheres includes the following steps:

[0020] (1) After stirring for 3 h, the ternary phase (W / O / W) emulsion system obtained in step one is immersed and left to stand with anhydrous ethanol;

[0021] (2) The precipitate is placed in an oven and dried at 80°C to obtain hollow SiO2microspheres, designated as SHMs.

[0022] Preferably, the culture of the bacterial suspension includes the following steps:

[0023] (1) Selecting oil-loving bacteria Al: Acinetobacter lwoffii; BTS: Bacillus thuringiensis; A6: Pseudomonas aeruginosa; F1: Nocardioides flavus; SP: Penicillium oxalicum;

[0024] After activation, pick 80-120 μL of each of the five bacteria and inoculate them into five sterile nutrient broth media, and perform oscillation propagation culture at 37°C and 120 r / min;

[0025] (2) After 48 h, observe whether it becomes turbid, and then take 50 mL of each and place them into 250 mL conical flasks to prepare a mixed bacterial culture medium;

[0026] (3) Observe the number of bacterial species by the hemocytometer method, and ensure that the number of bacterial species reaches 1×10 8 cfu / mL or above; store at 4°C for later use.

[0027] Preferably, the preparation of the single-hole SiO2hollow sphere microbial bioreactor includes the following steps:

[0028] (1) Take 1 g of single-hole SiO2hollow spheres SHMs and place them in a clean culture dish, pour 10 mL of mixed bacterial culture medium into the culture dish, and immerse the SHMs at room temperature for 24 h to allow them to grow autonomously inside and outside the SHMs;

[0029] (2) Filter the SHMs, and rinse the SHMs with a small amount of distilled water multiple times, the purpose being to remove most of the microorganisms on the surface of the SHMs and to retain as many microorganisms as possible inside the SHMs;

[0030] (3) Dry the rinsed SHMs at room temperature and designate them as Microbe@SHMs.

[0031] Preferably, in the aforementioned step (2), the solution of the nano-sized SiO2 particles is repeatedly sprayed on the Microbe@SHMs for 12 times, each time with 5 mL of distilled water.

[0032] Preferably, the preparation of the nano-sized SiO2 particles comprises the following steps:

[0033] (1) 2 mL of methyltrimethoxysilane is dissolved in 20 mL of distilled water and 40 mL of anhydrous ethanol, and stirred for 1 h;

[0034] (2) 0.1 g of ammonia water is added to the above-mentioned liquid, and stirred at 800 r / min for 24 h to form a turbid liquid, and at this time the white turbidity in the liquid is the nano-sized SiO2 particles formed by hydrolysis.

[0035] Preferably, the preparation of the single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure comprises the following steps:

[0036] (1) The solution containing nano-sized SiO2 particles obtained in step five is sprayed on the Microbe@SHMs for multiple times in small amounts;

[0037] (2) Drying is performed in an oven at 30℃ to obtain a single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure having a hydrophobic shell, which is named as M / Microbe@SHMs.

[0038] Preferably, in the aforementioned step (1), 5 mL of the solution containing nano-sized SiO2 particles is repeatedly sprayed on 1 g of the material for four times.

[0039] Preferably, the concentration of Na2SiO3 is 22.6 wt%, and in order to directionally control the preparation of single-hole SiO2 hollow spheres, 15 wt%, 22.6 wt%, and 30 wt% of sodium silicate solution are prepared under different conditions.

[0040] Preferably, the amount of the added polymer sodium polyacrylate is 8 mL, and in order to directionally control the preparation of single-hole SiO2 hollow spheres, the amount of PAAS is added to be 0, 3, 5, 8, 10, and 15 mL, respectively.

[0041] Preferably, the preparation of single-hole SiO2 hollow spheres is performed under the following conditions: when the concentration of Na2SiO3 is 22.6 wt% and the amount of added PAAS is 8 mL, the solution is stirred in IWP for 3 h, and the single-hole SiO2 hollow spheres are prepared by washing with anhydrous ethanol for 10 times and rinsing with distilled water for 8 times, and drying.

[0042] The application also discloses the single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure prepared by the preparation method.

[0043] Application of core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor in oil-water separation and biodegradation.

[0044] The present application has the following beneficial effects:

[0045] The present application selects SiO2 as a base material, which is green, environmentally friendly and has good biocompatibility. The single-hole SiO2 hollow sphere is prepared by changing the conditions for directional regulation, and the self-screened oil-loving bacteria are loaded in the hollow sphere to form a bioreactor as part of the core. The shell part uses silane hydrolysis to generate nano-sized SiO2 particles, which are sprayed on the surface of the bioreactor to form a hydrophobic shell. The material has excellent selective adsorption capacity and excellent adsorption capacity for oil-containing wastewater. It shows super strong demulsification ability for emulsified oil. The present application explores the degradation performance of diesel oil, and the core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor shows degradation ability for 5% diesel oil. The material has a core-shell structure, and the core has a large space to load a large amount of microorganisms, which has excellent degradation ability. The presence of the core-shell structure protects the microorganisms from direct contact with the environment and creates a specific survival environment for them, and ensures that the microorganisms will not leak. Through performance testing of the material, the material has excellent oil-water separation and biodegradation performance, and exhibits strong chemical stability in extreme environments, and can be recycled multiple times. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 is a preparation route diagram of the core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor of the present application;

[0047] Figure 2 is a process diagram of changing conditions for directional regulation of the core-shell structure single-hole SiO2 hollow sphere (SHMs) of the present application;

[0048] Figure 3 (a-a”) is a scanning electron microscope image, an optical microscope image and a transmission electron microscope image of the hollow structure of the SHMs of the present application;

[0049] Figure 3 (b-b’) is a scanning electron microscope image and an optical microscope image of the SHMs loaded with microorganisms to form a bioreactor Microbe@SHMs of the present application;

[0050] Figure 3 (c-c”) is a scanning electron microscope image and an element analysis diagram of M / Microbe@SHMs of the present application;

[0051] Figure 4 (a-b) is a hydrophobic angle of Microbe@SHMs and a selective adsorption diesel oil diagram of the present application;

[0052] Figure 4 (c-d) are the hydrophobic angle and selective adsorption of diesel of M / Microbe@SHMs of the present application;

[0053] Figure 4 (e) is the instantaneous adsorption capacity of diesel of M / Microbe@SHMs of the present application;

[0054] Figure 4 (f) is the self-cleaning capacity of M / Microbe@SHMs of the present application;

[0055] Figure 5 (a) is the oil-water separation of M / Microbe@SHMs of the present application for dispersed oil-containing oily wastewater;

[0056] Figure 5 (b) is the oil-water separation of M / Microbe@SHMs of the present application for emulsified oil-containing oily wastewater;

[0057] Figure 5 (c-c”) are the separation capacity of M / Microbe@SHMs of the present application for water-in-oil emulsified oil and the particle size distribution before and after separation;

[0058] Figure 5 (d-d”) are the separation capacity of M / Microbe@SHMs of the present application for oil-in-water emulsified oil and the particle size distribution before and after separation;

[0059] Figure 6 Adsorption capacity of M / Microbe@SHMs of the present application for organic solvents;

[0060] Figure 7 (a) is the removal and degradation rate of M / Microbe@SHMs of the present application;

[0061] Figure 7 (b-c) are the degradation component analysis of M / Microbe@SHMs of the present application for 24-240h;

[0062] Figure 7 (d-e) are the degradation component analysis of M / Microbe@SHMs of the present application for 24-240h;

[0063] Figure 8 (a) is the thermal stability test of M / Microbe@SHMs of the present application;

[0064] Figure 8 (b) is the test of M / Microbe@SHMs of the present application under extreme environment. DETAILED DESCRIPTION

[0065] The following examples facilitate a better understanding of the present application, but do not limit the present application. The experimental methods in the following examples are all conventional methods, unless otherwise specified. The test materials used in the following examples are all commercially available, unless otherwise specified.

[0066] Figure 1 is a preparation route map of the core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor of the present application.

[0067] Example 1

[0068] Preparation of single-hole SiO2 hollow spheres:

[0069] The silica microspheres were prepared by a ternary phase (W / O / W) microemulsion system, and the ternary phase was an inner water phase, an oil phase and an outer water phase. The inner water phase (IWP) was 36 mL (15 wt%, 22.6 wt%, 30 wt%) of a sodium silicate solution, and polyacrylic acid sodium SP (0, 3, 5, 8, 10, 15 mL). The oil phase (OP) was 36 mL of n-hexane, 0.75 g of Tween 80, and 0.75 g of Span 80. The outer water phase (OWP) was 100 mL of a 2 mol / L NH4HCO3 aqueous solution. First, the OP was added to the IWP and emulsified at 8000 rpm for 5 min, and then the mixed solution was added to the OWP and stirred vigorously for 3 h; distilled water was added and left to stand for 2 h, and the water was replaced 4 times; then the precipitate was soaked in anhydrous ethanol and left to stand; finally, the precipitate was placed in an oven at 80°C for drying, to obtain hollow SiO2 microspheres, designated as SHMs.

[0070] As Figure 2 Preparation of single-hole SiO2 hollow spheres by changing the adjustment and directional control.

[0071] Figure 3 (a-a”) are scanning electron microscope images, optical microscope images and transmission electron microscope images of the SHMs hollow spheres of the present application, proving that the SHMs are hollow structures and the shell is thin.

[0072] Example 2

[0073] Preparation of single-hole SiO2 hollow sphere loaded microbial bioreactor:

[0074] First, five kinds of microorganisms independently screened by the inventors were mixed and cultured under harsh conditions:

[0075] (1) Special oil-loving bacteria Al: Lofflerella pseudomallei; BTS: Bacillus thuringiensis; A6: Pseudomonas aeruginosa; F1: Nocardia flavus; SP: Penicillium oxalicum;

[0076] (2) After activation, about 100 μL of each of the five kinds of bacteria was inoculated into five sterile nutrient broth media and cultured at 37°C with shaking at 120 r / min for proliferation;

[0077] (3) After 48h, observe whether it becomes turbid, and then take 50mL each into 250mL conical flask to prepare mixed bacteria culture medium by mixing;

[0078] (4) Observe the number of bacteria by hemocytometer method, and ensure that the number of bacteria reaches 1×10 8 cfu / mL; store at 4℃ for later use.

[0079] Take 1.0g of the prepared SHMs and put into 10mL of bacteria suspension to perform self-growth for 24h, then filter the SHMs and rinse with distilled water for multiple times, so as to remove most of the microorganisms on the surface of the SHMs and try to retain the microorganisms inside the SHMs; the weight difference before and after loading is the mass of the microorganisms; the hollow SiO2 microspheres loaded with microorganisms are named as Microbe@SHMs.

[0080] As Figure 3 (b-b') The scanning electron microscope image of the Microbe@SHMs hollow spheres of the application and the optical microscope image of the color of the microorganisms from outside to inside; it can be seen that the microorganisms are loaded inside the hollow spheres, which proves that the microorganisms are successfully loaded inside the SHMs.

[0081] Example 3

[0082] Preparation of the core-shell structure single-hole SiO2 hollow sphere loaded with microorganisms bioreactor:

[0083] Take 2mL of methyltrimethoxysilane and dissolve in 20mL of distilled water and 40mL of anhydrous ethanol, add 0.1mL of ammonia water, and stir at 800r / min for 24h to form a turbid liquid. The liquid is sprayed on the Microbe@SHMs in small amounts and multiple times to obtain hydrophobic M / Microbe@SHMs, and the material obtained at this time is named as M / Microbe@SHMs.

[0084] Figure 3 (c-c”) is the scanning electron microscope image and element analysis chart of the M / Microbe@SHMs of the application, which proves that the core-shell structure M / Microbe@SHMs is successfully prepared.

[0085] Example 4

[0086] Application of the core-shell structure single-hole SiO2 hollow sphere loaded with microorganisms bioreactor of the application in selective adsorption.

[0087] Take 50mL of distilled water and put it into a 100mL culture dish, and dye the diesel oil with oil red O. The diesel oil is small in density and floats on the surface, and is taken and put into water, and the material selectively adsorbs diesel oil.

[0088] As Figure 4 (a-b) show that the hydrophobic angle of the Microbe@SHMs of the application is 0°, and the Microbe@SHMs have no hydrophobic ability and cannot adsorb the diesel oil added within 3 min.

[0089] As Figure 4 (c-d) show that the hydrophobic angle of the M / Microbe@SHMs of the application is 151.8°, and the M / Microbe@SHMs have superhydrophobicity and can selectively adsorb the diesel oil added within 60 s.

[0090] Figure 4 (e) is a schematic diagram of the instantaneous adsorption capacity of the M / Microbe@SHMs of the application to diesel oil, as Figure 4 (e) shows that the M / Microbe@SHMs can adsorb the oil completely within 1.04 s.

[0091] Figure 4 (f) is a schematic diagram of the self-cleaning ability of the M / Microbe@SHMs of the application, as Figure 4 (e) shows that the M / Microbe@SHMs have strong anti-adhesion and are convenient to clean and reuse.

[0092] Example 5

[0093] Application of the core-shell structure single-hole SiO2 hollow ball loaded microbial bioreactor of the application in oil-water separation.

[0094] As Figure 5 (a) shows that the M / Microbe@SHMs of the application can easily separate the dispersed oil from water through a simple self-made device;

[0095] As Figure 5 (b) shows that a small amount of the M / Microbe@SHMs of the application is put into emulsified oil, and the emulsified oil is separated by gently shaking, and the M / Microbe@SHMs have demulsification ability.

[0096] Example 6

[0097] Application of the core-shell structure single-hole SiO2 hollow ball loaded microbial bioreactor of the application in adsorption of organic solvents.

[0098] 1g of M / Microbe@SHMs is weighed and put into different organic solvents for adsorption saturation, and then filtered and weighed to obtain the adsorption saturation capacity. All the adsorption experiments are performed three times.

[0099] As Figure 6 shown, the M / Microbe@SHMs of the application have strong adsorption capacity to different organic solvents, and can adsorb 3-6 times of their own weight.

[0100] Example 7

[0101] Application of the core-shell structure single-hole SiO2 hollow ball loaded microbial bioreactor in biodegradation.

[0102] Through diesel adsorption degradation experiment, the adsorption concentration of diesel at 257nm wavelength was determined by ultraviolet spectrophotometer to evaluate the adsorption performance of diesel. Diesel with concentrations of 1, 2, 3, 4, 5, 6, 7, 8g / L was configured for test. Diesel was analyzed by ultraviolet spectrophotometry, and a standard curve of diesel was drawn. All adsorption experiments were carried out for three times, and the average value was used for UV test. According to the value of absorbance, the residual concentration was measured by fitting with the standard curve.

[0103] At room temperature, 0.1g M / Microbe@SHMs was placed in saturated diesel for 24h, 72h, 120h, 168h, 216h and 240h to degrade diesel with maximum adsorption capacity; the change of degradation efficiency of M / Microbe@SHMs with time was explored; and the adsorption of diesel by free bacteria without fixed material was observed.

[0104] Through diesel adsorption degradation experiment, the adsorption concentration of diesel at 257nm wavelength was determined by ultraviolet spectrophotometer to evaluate the adsorption performance of diesel. GC-MS (Thermo Scientific TSQ 9610, Thermo Fisher Scientific (China) Co., Ltd.) was used for quantitative analysis, and the degradation rate was calculated by standard curve.

[0105] As Figure 7 (a), it can be seen that the removal rate of diesel by M / Microbe@SHMs can reach 86.3%, while the removal rate of diesel by free bacteria can reach 48.2%, and the removal rate of diesel by M / Microbe@SHMs has obvious increase.

[0106] As Figure 7 (b-e), it can be clearly seen from the GC-MS test that the peak value of complex alkanes decreases, and the smaller the peak value decreases, the better the degradation performance of diesel by microorganisms.

[0107] From Figure 7 (b-c), it can be seen that the peak value of M / Microbe@SHMs 24h-240h decreases obviously, Figure 7 (d-e), the peak value of free bacteria does not decrease much, indicating that the effect of the material immobilized microorganism of the application on degradation of diesel is better.

[0108] As Figure 8 (a), M / Microbe@SHMs has good thermal stability, and the thermal loss at 800℃ is only 15.71%.

[0109] As Figure 8 (b), M / Microbe@SHMs in the case of pH = 1 and pH = 14, the material stability test can be seen that the material in the strong acid and strong alkali extreme environment still has good stability; in the case of high concentration of salt solution and simulated seawater also showed good stability.

[0110] The present application relates to the directional regulation to ternary phase microemulsion system to prepare single-hole SiO2 hollow sphere, internal load microorganism forms a bioreactor; the hydrophobic lipophilic material is coated to the SiO2 hollow sphere to form the single-hole SiO2 hollow sphere load microorganism bioreactor with core-shell structure.The present application uses green and environment-friendly, excellent chemical stability SiO2 as base material, prepares single-hole SiO2 hollow sphere by directional regulation method, loads microorganism as part of the core; the shell part adopts the hydrolysis of silane to generate SiO2 nanoparticles, and the material hydrophobic lipophilic performance is endowed by spraying in the outer layer of the core in a little multiple spraying mode, and the core-shell structure bioreactor with selective adsorption and in-situ biodegradation is prepared.At the same time, the core-shell structure bioreactor constructed by the present application plays a key role in protecting microorganisms and preventing microorganism leakage as an independent and closed specific space, and through the application research, the core-shell structure single-hole SiO2 hollow sphere belongs to μm level, the size is small, has low surface energy, large specific surface area, thereby improving the adsorption capacity, excellent oil-water separation capacity and emulsified oil demulsification capacity, and the material has good degradation characteristics to the adsorbed oil by loading microorganism, and the material presents strong thermal stability and tolerance to the surrounding adverse environment.

[0111] The above embodiment is not a limitation of the present application, and the present application is not limited to the above examples, and the changes, modifications, additions or replacements made by the person skilled in the art within the technical solution range of the present application also belong to the protection scope of the present application.

Claims

1. A method for preparing a core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor, characterized in that, Comprising the following steps: Step one: preparation of ternary phase W / O / W microemulsion; the preparation of ternary phase W / O / W microemulsion comprises the following steps: (1) Preparation of inner water phase IWP: take 36 mL of sodium silicate solution, mix with 8 mL of sodium polyacrylate solution, and stir well to dissolve the sodium silicate in the solution; (2) Preparation of oil phase OP: take 36 mL of n-hexane, add 0.75 g of Tween 80 and 0.75 g of Span 80, and mix well; (3) Take 100 mL of 2 mol / L ammonium bicarbonate solution as the outer water phase OWP; (4) Preparation of ternary phase W / O / W: first emulsify the oil phase OP in the inner water phase IWP at 8000 rpm for 5 min, then add the mixed solution to the outer water phase OWP and stir for 3 h; Step two: preparation of single-hole SiO2 hollow sphere; the preparation of single-hole SiO2 hollow sphere comprises the following steps: (1) After stirring for 3 h, the ternary phase W / O / W emulsion system obtained in step one is immersed in anhydrous ethanol and left to stand; (2) Put the precipitate into an oven and dry at 80℃ to obtain single-hole SiO2 hollow sphere SHMs; Step three: culture of bacterial suspension; Step four: preparation of single-hole SiO2 hollow sphere loaded microbial bioreactor; the preparation of single-hole SiO2 hollow sphere loaded microbial bioreactor comprises the following steps: (1) Take 1 g of single-hole SiO2 hollow sphere SHMs and put it into a clean culture dish, take 10 mL of mixed bacteria culture medium and pour it into the culture dish, soak the SHMs in room temperature for 24 h, and let it grow spontaneously inside and outside the SHMs; (2) Filter the SHMs, rinse the SHMs with a small amount of distilled water several times to remove most of the microorganisms on the surface of the SHMs; (3) Dry the rinsed SHMs at room temperature to obtain single-hole SiO2 hollow sphere loaded microbial bioreactor Microbe@SHMs; Step five: preparation of nano-sized SiO2 particles; the preparation of nano-sized SiO2 particles comprises the following steps: (1) Take 2 mL of methyltrimethoxysilane and dissolve it in 20 mL of distilled water and 40 mL of anhydrous ethanol, and stir well for 1 h; (2) Add 0.1 g of ammonia water to the above liquid and stir at 800 r / min for 24 h to form a turbid liquid, obtaining nano-sized SiO2 particles formed by hydrolysis; Step six: preparation of single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure; the preparation of single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure comprises the following steps: (1) Spray the solution containing nano-sized SiO2 particles obtained in step five on the single-hole SiO2 hollow sphere loaded microbial bioreactor Microbe@SHMs several times; (2) Dry in an oven at 30℃ to obtain single-hole SiO2 hollow sphere loaded microbial bioreactor with core-shell structure M / Microbe@SHMs.

2. The preparation method of the core-shell structure monoporous SiO2 hollow sphere loaded microbial bioreactor according to claim 1, characterized in that: The culture of bacterial suspension comprises the following steps: (1) Oil-loving bacteria Al: Acinetobacter lwoffii; BTS: Bacillus thuringiensis; A6: Pseudomonas aeruginosa; F1: Nocardioides flavus; SP: Penicillium oxalicum; After activation, pick up the five kinds of bacteria, 80 μL-120 μL each is inoculated in five sterile nutrient broth medium, 37℃, 120 r / min for shaking culture; (2) 48 h after observation whether it is turbid, and then 50 mL each is put into 250 mL conical flask for mixing to prepare mixed bacteria culture medium; (4) The number of bacterial strains is observed by a blood cell counting plate method to ensure that the number of bacterial strains reaches 1 x 10 8 cfu / mL or above; and the bacterial strains are stored at 4 ℃ for later use.

3. The preparation method of the core-shell structure monolithic SiO2 hollow sphere loaded microbial bioreactor according to claim 2, characterized in that: The sodium silicate solution has a concentration of 15 wt%, 22.6 wt% or 30 wt%.

4. A core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor prepared by the preparation method in any one of claims 1-3.

5. Application of the core-shell structure single-hole SiO2 hollow sphere loaded microbial bioreactor in claim 4 in oil-water separation and biodegradation.

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