CN110452901B

CN110452901B - Immobilized biological reaction filter plate and preparation method and application thereof

Info

Publication number: CN110452901B
Application number: CN201910755332.3A
Authority: CN
Inventors: 孙有俊; 孙冬梅; 范彩云; 鲍芳丽
Original assignee: Wuhu Yize Small And Medium Enterprise Public Service Co ltd
Current assignee: WUHU YIZE SMALL AND MEDIUM ENTERPRISE PUBLIC SERVICE Co.,Ltd.
Priority date: 2019-08-15
Filing date: 2019-08-15
Publication date: 2021-07-16
Anticipated expiration: 2039-08-15
Also published as: CN110452901A

Abstract

The invention discloses an immobilized bioreaction filter plate and a preparation method and application thereof, the immobilized bioreaction filter plate comprises a deposition glass plate and microorganisms, the porous deposition glass plate formed after glass molten drop injection, cooling and deposition is used as a support carrier, the specific surface area under the same volume is large, the contact area between the loaded PVA film and a substrate liquid is also large, the microorganisms are fixed in the PVA film layer, the bioavailability is greatly improved, and the treatment efficiency is improved. The pore size of the deposited glass plate is moderate, the fluidity of the infiltration filtration and the hydraulic retention time are considered, and the treatment time of the substrate in unit volume is reduced while the ammonia nitrogen elimination rate is ensured. The modified PVA film has stable microorganism fixing effect and little influence on the activity of microorganisms. When the immobilized biological reaction filter plate is applied to sewage treatment, the number of the filter plate layers can be flexibly regulated according to the ammonia nitrogen level of sewage, the treatment strength is changed, unnecessary waste is reduced, high-ammonia nitrogen sewage is efficiently treated, and the treatment cost is reduced.

Description

Immobilized biological reaction filter plate and preparation method and application thereof

Technical Field

The invention relates to the field of immobilized microorganisms, in particular to an immobilized biological reaction filter plate and a preparation method and application thereof.

Background

The microorganism immobilization technology is a biological immobilization technology which is used for immobilizing dominant microorganisms on a specific carrier in a high density by a physical or chemical method, can keep activity for a certain period of time and can meet specified requirements under suitable growth conditions. The basic starting point of the microbial immobilization technology is to improve the efficiency and stability of the treatment process based on the dominant microbial population, to increase the microbial density per unit volume, and to eliminate the problem of microbial loss. Compared with the traditional activated sludge method, the method has the advantages that the microbial biomass is low, sludge bulking and loss are easy to occur, the adaptability to the water quality and water quantity of the wastewater is poor, and the like, and the microbial immobilization technology has very obvious advantages when being used for treating the wastewater:

(1) the dominant microorganisms are fixed in a certain space at high density, so that the concentration of the microorganisms in the bioreactor is greatly improved, the reaction speed is improved, the reaction time is shortened, and the occupied area and the volume of a treatment facility are reduced. (2) Can mix and embed nitrobacteria and denitrifying bacteria commonly used in biological denitrification, and realize the aim of simultaneously fixing different types of microorganisms in the same reactor. (3) The microorganism is fixed in a carrier, which is beneficial to improving the adaptability of the microorganism to the change of the surrounding environment and increasing the impact load resistance capability and the tolerance to toxic substances of the reactor in the sewage and wastewater treatment process. (4) The immobilized microorganisms can quickly realize solid-liquid separation after reaction, and the amount of the residual sludge is small. Fifthly, the stability is strong, the treatment efficiency is high, and high-efficiency strains can be purified and maintained.

At present, a plurality of methods for preparing immobilized microorganisms exist, and any technology which can limit the microorganisms in a certain space and keep certain activity can be used for preparing immobilized dominant microorganisms. Generally, the following methods are used for preparing immobilized microorganisms: embedding method, adsorption method, cross-linking method, covalent binding method. The adsorption method mostly adopts porous materials such as diatomite and the like to physically adsorb microorganisms for fixation, the binding force is weak, and the activity of the microorganisms is high because no chemical treatment is carried out; the cross-linking method is to make the microbial cells connected into a net structure by covalently bonding a cross-linking agent with amino, hydroxyl, sulfydryl and other groups on the surface of the microbes for cross-linking, but the method has the disadvantages of violent chemical reaction, high toxicity of the cross-linking agent and great loss of microbial activity. The covalent bonding method is a method for fixing microorganisms by utilizing chemical bond connection of functional groups (such as amino, carboxyl, sulfydryl and the like) on the surfaces of microbial cells and carrier surface groups, so that the bonding is tight, the stability is good, but the reaction is violent during the group bonding, the operation is complex and difficult to control, and the activity of the fixed microorganisms is lower. The embedding method adopts a carrier to embed the microorganism, the reaction is soft, the mechanical strength of the prepared immobilized pellet is high, the bonding strength of the carrier and the microorganism is moderate, and the activity of the microorganism is high, so that the method is the most commonly used method in the field of immobilized microorganisms at present.

Carriers for entrapping immobilization of microorganisms can be roughly classified into two main groups: one is natural polymer gel carrier, such as agar, carrageenan, sodium alginate, etc.; the natural polymer gel carrier is mainly represented by sodium alginate, and is a microorganism immobilization carrier which is widely applied at present. It is extracted from natural seaweed, and has the advantages of no toxicity to organism, high mass transfer performance, low cost, low strength, no suitability for use in high aeration condition and easy decomposition in anaerobic condition. Another class is organic polymer gel supports such as PVA, polyaluminium sulfate, silica gel, and the like, of which PVA is the most representative. Compared with natural polymer gel carrier, the mechanical strength of the immobilized particles made of the organic polymer gel carrier is higher than that of the immobilized particles made of the natural polymer gel carrier, but the mass transfer performance of the immobilized particles is inferior to that of the immobilized particles made of the natural polymer gel carrier, and the immobilized particles have higher activity to microorganisms after being embedded and are easy to inactivate the immobilized microorganisms.

In addition, most of the traditional embedded and immobilized microorganisms are porous pellet preparations, the specific surface area is small, the contact area with a substrate is small, the microorganisms are embedded and fixed in a high-molecular carrier, the treatment effect strongly depends on or is limited by the mass transfer performance of the carrier, the mass transfer performance of the embedded pellet formed by curing and crosslinking the high-molecular carrier is poor, and the treatment efficiency of the microorganisms cannot be maximized. Meanwhile, a large amount of immobilized microbial agents are needed as fillers when the substrate solution in unit volume is continuously treated, the hydraulic retention time is longer, the treatment effect is slower, and the efficiency is lower.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at various defects existing in the conventional immobilized microbial preparation and preparation process, the invention provides an immobilized biological reaction filter plate, which adopts a porous deposition glass plate as a support carrier, increases the contact area with a substrate, has high mechanical strength, is adhered and fixed with microbes on the inner surface and the outer surface, and has high microbial utilization rate, excellent mass transfer performance and high treatment efficiency when continuous reaction is carried out.

In order to solve the technical problems, the invention provides the following technical scheme:

the utility model provides an immobilization biological reaction filter plate, contains deposit glass board and sewage treatment microorganism, deposit the glass board by glass molten drop after the rapid condensation and bond and form, condensation glass particle average particle diameter is 0.4~1.1mm, piles up between the glass particle and forms the hole, and the aperture of hole scope is 149~674 mu m, the thickness of deposit glass board is 1~10cm, and the even load of deposit glass board inside and outside surface has one deck PVA membrane, the thickness of PVA membrane is 56~163 mu m, and the PVA membrane internal fixation has sewage treatment bacterium and/or sewage treatment alga.

Preferably, the sewage treatment bacteria are nitrifying bacteria, nitrosobacteria and denitrifying bacteria, the sewage treatment algae comprise one or more of chlorella, blue algae, diatom, spirulina, rhodobacter, chlorella, botryococcus and scenedesmus, the light transmittance of the deposition glass plate is 75-90%, the polymerization degree of PVA is 2000-6000, and the alcoholysis degree is 87-89%.

The preparation method of the immobilized biological reaction filter plate comprises the following specific steps:

(1) heating the glass raw materials to 700-950 ℃, preserving heat, completely melting, and preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device, wherein the jet deposition process parameters are as follows: taking 5-10 MPa high-pressure argon as atomizing gas, wherein the vertical spraying distance is 25-35cm, the inner diameter of a liquid guide pipe is 6-8 mm, the spraying angle is 45-60 degrees, a deposition disc is horizontally placed, the horizontal moving speed of the deposition disc is 2-4 mm/s, the vertical moving speed is 0.1-0.2 mm/s, the deposition disc horizontally reciprocates at the same speed every 100s until the thickness of the deposition layer reaches 1-10 cm, the deposition is stopped, and the deposition is immersed in cold water to be rapidly cooled to obtain a deposition glass plate;

(2) weighing 6-8 wt% of PVA, 2-4 wt% of nano-silica, 1-3 wt% of diatomite, 1-3 wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃ for heat preservation, slowly stirring and adding the nano-silica and the diatomite, uniformly stirring, ultrasonically degassing, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by using 1 XPBS, homogenizing, filtering by using single-layer gauze to obtain resuspended bacterial liquid, respectively centrifuging the resuspended bacterial liquid or algae culture suspension at 2500rpm for 10min, respectively taking bacterial sediment or algae sediment for storage at 4 ℃, and taking the bacterial sediment and/or the algae sediment as sewage treatment microorganisms for fixation;

(4) mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 4-20: 1, and magnetically stirring at 250-500 rpm for 10-20 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing for 5-15 min at 10-20 kHz; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering at the air pressure of 0.4-0.8 MPa for 5-20 min;

(5) at the temperature of 4 ℃, the CaCl with the content of 0.5 to 0.8wt percent is added₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 0.5-1.5 h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for solidification and crosslinking for 10-16 h, the solidification and crosslinking are carried out, then, the upflow type filtration and washing are carried out for 15-25 min through distilled water, the immobilized biological reaction filter plate is obtained, and the immobilized biological reaction filter plate is obtainedThe biochemical reaction filter plate is placed in phosphate buffer solution with the temperature of 4 ℃ and the pH value of 7.2 for storage.

Preferably, the total concentration of the bacteria of the nitrifying bacteria, the nitrosobacteria and the denitrifying bacteria in the bacterial sludge containing the sewage treatment bacteria is 1.56-5.98 x 10⁷The cell density of algae in the algae culture suspension is 1.22-6.35 multiplied by 10⁵Per mL; when the fixing sewage treatment microorganisms comprise thallus precipitates and algae precipitates, the wet weight ratio of the thallus precipitates to the algae precipitates is 1-10: 1.

Preferably, the step (1) further comprises a bacterial sludge enrichment and domestication step of the sewage treatment bacteria, which is as follows:

(A) domesticating and enriching sewage treatment bacteria by adopting sterile initial culture solution, inoculating activated sludge into the culture solution according to the MLSS of 2.19-3.03 g/L in a fermentation tank, and stirring and culturing at 50-100 rpm to ensure that the culture conditions are constant: the temperature is 14-17 ℃, the pH is 7.0-7.5, and the dissolved oxygen is 2.0-3.0 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L;

(B) culturing until MLSS reaches 8g/L, then replacing the domestication culture solution for half an hour every 6-8 hours, precipitating for 20-40 min before replacing the solution, then removing the supernatant, adding an equivalent amount of sterile inorganic culture solution, and performing domestication culture for 48-72 hours; the concentrations of ammonium nitrogen and chemical oxygen demand in the domestication culture solution are increased progressively along with the replacement times on the basis of the initial culture solution, and each time, the concentrations are increased progressively by 50-70 mg/L;

(C) and centrifuging after acclimatization and culture to obtain a precipitate, washing the precipitate with 10 times of normal saline for three times, discarding the supernatant, counting, identifying, and storing at 4 ℃ to obtain the bacterial sludge of the sewage treatment bacteria.

Preferably, the initial culture solution further comprises 2-5 g/L of gel particles, the particle size of the gel particles is 1-3 mm, and the gel is one or more of sodium alginate gel, agar gel, carbomer gel, xanthan gum, agarose gel and polyacrylamide gel.

A method for treating high ammonia nitrogen sewage by applying the immobilized biological reaction filter plate comprises the following specific steps:

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed;

(2) performing solid-liquid separation on the high ammonia nitrogen sewage, filtering the liquid by coarse sand of 20-30 cm, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized biological reaction filter plate in the liquid level, maintaining the liquid level at 10-30 cm, filtering the liquid layer by layer through the immobilized biological reaction filter plates, and keeping the hydraulic retention time of each layer of immobilized biological reaction filter plate at 0.3-1 h;

(3) after the sewage liquid is injected, continuously giving illumination to the fluorescent lamp for 24 hours, wherein the illumination intensity is 1000-2500 Lx;

(4) and (3) detecting the ammonia nitrogen value and the chemical oxygen demand of the purified effluent of the sewage treatment reactor, and discharging the effluent after meeting the national standard.

Preferably, the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, one layer is arranged at the ammonia nitrogen value of less than or equal to 200mg/L, two layers are arranged at 200-400 mg/L, three layers are arranged at 400-600 mg/L, and the like; carrying out aeration operation before solid-liquid separation of the high ammonia nitrogen sewage; and (3) respectively illuminating each layer of the immobilized biological reaction filter plate in the step (3), wherein the illumination intensity is 1500 Lx.

The invention has the following beneficial effects:

1. the porous deposition glass plate formed after glass molten drop spraying, cooling and depositing is used as a supporting carrier, the specific surface area is large under the same volume, the contact area with substrate liquid is large after the PVA film is loaded, the microorganisms are fixed in the PVA film layer, the bioavailability is greatly improved, and the treatment efficiency is improved. The pore size of the deposited glass plate is moderate, the fluidity of the infiltration filtration and the hydraulic retention time are considered, and the treatment time of the substrate in unit volume is reduced while the ammonia nitrogen elimination rate is ensured.

2. The glass material texture is hard at normal temperature for need not consider the mechanical strength of embedding carrier behind the load PVA membrane, adopt the PVA of high polymerization degree as embedding material, viscosity is high, and the cohesiveness is strong, can be able to bear or endure to erode behind the formation PVA membrane, is difficult for droing, adds ductility and the mechanical strength that can show increase PVA membrane after the modification of nanometer silica, prevents that PVA membrane from tearing.

3. PVA has good film forming property, a PVA film layer loaded on the surface of a deposition glass plate is thin, and the defect of poor mass transfer property of PVA materials is overcome by adding sodium alginate and diatomite; sodium alginate and diatomite are added into the PVA film as adsorption and fixation components to increase the fixation amount of microorganisms, the microorganism fixation effect is stable, the loss is not easy, the fixation has little influence on the activity of the microorganisms, and the high activity of the microorganisms can be maintained for a long time.

4. When the immobilized biological reaction filter plate is applied to sewage treatment, the number of the filter plate layers can be flexibly regulated according to the ammonia nitrogen level of sewage, the treatment strength is changed, unnecessary waste is reduced, high-ammonia nitrogen sewage is efficiently treated, and the treatment cost is reduced.

5. By gradually increasing the ammonia nitrogen load level of the sewage treatment bacteria, the anhydrous treatment bacteria are gradually domesticated and enriched, the ammonia nitrogen conversion activity of the bacteria is improved while the number of the bacteria is increased, and the high-activity sewage treatment bacteria are obtained.

6. When the bacteria are mainly nitrifying or nitrosating bacteria, aerobic nitrification or nitrosating reaction is mainly carried out, oxygen can be provided for the nitrification or nitrosating reaction due to aeration and co-embedding of the algae, the nitrification or nitrosating reaction rate is improved, meanwhile, the algae can also fix ammonia nitrogen and phosphorus to carry out sewage purification, the hydraulic retention time can be reduced under the double purification treatment of the algae and the bacteria, and the sewage treatment efficiency is obviously improved. When the anaerobic condition is adopted, the activity of denitrifying bacteria is improved, and sewage treatment can be carried out under the condition of non-aeration operation and algae.

Drawings

FIG. 1 is SEM electron microscope image of the surface of immobilized biological reaction filter plate.

Detailed Description

The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.

Example 1: the immobilized biological reaction filter plate is prepared and applied according to the following method:

preparation and prefabrication of raw materials

The degree of polymerization and alcoholysis of the pristine PVA was 2000%.

Enriching and domesticating bacterial sludge of sewage treatment bacteria:

(A) adopting sterile initial culture solution to domesticate and enrich bacteria for sewage treatment, inoculating activated sludge taken from a sewage treatment plant into the culture solution according to the mixed solution suspended solid concentration (MLSS) of 2.19g/L in a fermentation tank, stirring and culturing at 50rpm, and ensuring the culture conditions to be constant: the temperature is 14 ℃, the pH value is 7.0, and the dissolved oxygen is 2.0 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L;

(B) culturing until MLSS reaches 8g/L, replacing acclimation culture solution every 6 hours for half, precipitating for 20min before replacing, removing supernatant, adding equal amount of sterile inorganic culture solution, and acclimating and culturing for 48 h; the concentrations of ammonium nitrogen and chemical oxygen demand in the domesticated culture solution are increased progressively along with the replacement times on the basis of the initial culture solution, and each time, the concentrations are increased progressively by 50 mg/L;

(C) and centrifuging after acclimatization and culture to obtain a precipitate, washing the precipitate with 10 times of normal saline for three times, discarding the supernatant, counting, identifying, and storing at 4 ℃ to obtain the bacterial sludge of the sewage treatment bacteria. Through the culture identification (reference method (1) the separation and identification of yellow Jue nitrifying bacteria [ J]Aquatic science and technology information, 2004(3), 130-; (2) jiangxin combustion and anaerobic denitrifying bacteria separation and identification and preliminary study on denitrification effect of aquaculture wastewater [ D]The sewage treatment bacteria mainly comprise nitrobacteria, nitrosobacteria and denitrifying bacteria, and the total thallus concentration of the nitrobacteria, the nitrosobacteria and the denitrifying bacteria in the bacterial sludge is 1.56 multiplied by 10⁷Per gram. .

Secondly, preparing the immobilized biological reaction filter plate, which comprises the following steps:

(1) heating the colorless transparent glass raw material to 700 ℃ for heat preservation, preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device after the colorless transparent glass raw material is completely melted, wherein the jet deposition process parameters are as follows: using 5MPa high-pressure argon as atomizing gas, wherein the vertical spraying distance is 25cm, the inner diameter of a liquid guide pipe is 6mm, the spraying angle is 45 degrees, a deposition disc is horizontally placed, the horizontal moving speed of the deposition disc is 2mm/s, the vertical moving speed is 0.1mm/s, the deposition disc horizontally reciprocates at the same speed every 100s until the thickness of a deposition layer reaches 1cm, and the deposition is immersed in cold water to be rapidly cooled to obtain a deposition glass plate; the average diameter of the condensed glass particles is 0.4mm, pores are formed by stacking the glass particles, and the light transmittance of the deposited glass plate is 75%.

(2) Weighing 6 wt% of PVA, 2 wt% of nano-silica, 1 wt% of diatomite, 1 wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃, keeping the temperature, slowly stirring and adding the nano-silica and the diatomite, ultrasonically degassing after uniformly stirring, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by 1 XPBS, homogenizing, filtering with single-layer gauze to obtain resuspended bacterial liquid, centrifuging the resuspended bacterial liquid or algae suspension at 2500rpm for 10min, respectively collecting thallus precipitate or algae precipitate, storing at 4 deg.C, and using the thallus precipitate as sewage treatment microorganism for fixation.

(4) Mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 4:1, and magnetically stirring at 250rpm for 10 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing at 10kHz for 5 min; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering with the wind pressure of 0.4MPa for 5 min;

(5) at 4 ℃, the catalyst contains 0.5 wt% of CaCl₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the volume of the whole deposition glass plate, the filtering time is 0.5h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for solidification and crosslinking for 10h, the immobilization and crosslinking are carried out, then the upflow type filtration and washing are carried out for 15min by using distilled water, and the immobilization biological reaction filter plate is placed in a phosphate buffer solution at 4 ℃ and pH7.2 for storage and standby. The thickness of the PVA film on the surface of the deposited glass plate was measured to be 56. + -. 3.5 μm by using a Defelsko PositeTector 200C series ultrasonic coating thickness meter.

The immobilized biological reaction filter plate is applied to high ammonia nitrogen sewage treatment, and comprises the following specific steps:

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface in a sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 multiplied by PBS in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, the ammonia nitrogen value is less than or equal to 200mg/L and is provided with one layer, 200-400 mg/L is provided with two layers, 400-600 mg/L is provided with three layers, and by analogy, the ammonia nitrogen value of the high ammonia nitrogen sewage in the embodiment is 135.4mg/L, and one layer of the immobilized biological reaction filter plate is arranged for filtering treatment.

(2) Directly carrying out solid-liquid separation on the high ammonia nitrogen sewage, filtering the liquid by adopting coarse sand of 20cm, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized bioreaction filter plate on the liquid surface, maintaining the height of the liquid surface at 10cm, filtering the liquid by layers through the immobilized bioreaction filter plates, and keeping the hydraulic retention time of each layer of immobilized bioreaction filter plates at 0.3 h;

(3) and (3) detecting the ammonia nitrogen value and the chemical oxygen demand of the purified effluent of the sewage treatment reactor, and discharging the effluent after meeting the national standard.

Example 2: the immobilized biological reaction filter plate is prepared and applied according to the following method:

preparation and prefabrication of raw materials

Separately suspension culturing Chlorella to prepare sewage treatment algae suspension culture solution with algae cell density of 1.22 × 10⁵Stopping culturing when the strain is per mL;

the degree of polymerization of the PVA alone was 6000 and the degree of alcoholysis was 89%.

(1) heating the colorless transparent glass raw material to 950 ℃ for heat preservation, preparing the liquid glass into a deposited glass plate by adopting a multilayer spray deposition plate preparation device after the colorless transparent glass raw material is completely melted, wherein the spray deposition process parameters are as follows: using 10MPa high-pressure argon as atomizing gas, wherein the vertical spraying distance is 35cm, the inner diameter of a liquid guide pipe is 8mm, the spraying angle is 60 degrees, a deposition disc is horizontally placed, the horizontal moving speed of the deposition disc is 4mm/s, the vertical moving speed is 0.2mm/s, the deposition disc horizontally reciprocates at the same speed every 100s until the thickness of a deposition layer reaches 10cm, the deposition is stopped, and the deposition is immersed in cold water to be rapidly cooled to obtain a deposition glass plate; the average particle size of the condensed glass particles was 1.1mm, pores were formed by stacking the glass particles, and the light transmittance of the deposited glass sheet was 90%.

(2) Weighing 8wt% of PVA, 4wt% of nano-silica, 3wt% of diatomite, 3wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃, keeping the temperature, slowly stirring and adding the nano-silica and the diatomite, ultrasonically degassing after uniformly stirring, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by using 1 XPBS, homogenizing, filtering by using single-layer gauze to obtain resuspended bacterial liquid, respectively centrifuging the resuspended bacterial liquid or algae culture suspension at 2500rpm for 10min, respectively taking thalli sediment or algae sediment for storage at 4 ℃, and taking the algae sediment as sewage treatment microorganism for fixation;

(4) mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 20:1, and magnetically stirring at 500rpm for 20 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing for 15min at 20 kHz; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering for 20min under the air pressure of 0.8 MPa;

(5) at 4 ℃, the catalyst contains 0.8wt% of CaCl₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 1.5h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for solidification and crosslinking for 16h, after solidification and crosslinking, the deposition glass plate is filtered and washed by distilled water in an upflow type manner for 25min, so that an immobilized bioreaction filter plate is obtained, the immobilized bioreaction filter plate is placed in phosphate buffer solution at 4 ℃ and pH7.2 for standby, and the thickness of a PVA film on the surface of the deposition glass plate is 163 +/-7.8 mu m measured by adopting a Defelsk PositeTector 200C series ultrasonic coating thickness meter.

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, the ammonia nitrogen value is less than or equal to 200mg/L, one layer is arranged at 200-400 mg/L, two layers are arranged at 400-600 mg/L, and the rest is done in the same way. In this embodiment, the ammonia nitrogen value of the high ammonia nitrogen sewage is 388.4mg/L, and two layers of immobilized biological reaction filter plates are arranged.

(2) Aerating the high ammonia nitrogen sewage for 2 hours, then carrying out solid-liquid separation, filtering the liquid by adopting 30cm coarse sand, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized biological reaction filter plate on the liquid surface, maintaining the liquid surface height at 30cm, filtering the liquid layer by layer through the immobilized biological reaction filter plates, and keeping the hydraulic retention time of each layer of immobilized biological reaction filter plates at 1 hour;

(3) after the sewage liquid is injected, the single light source of the fluorescent lamp is continuously illuminated for 24 hours, and the illumination intensity is 1000 Lx;

Example 3: the immobilized biological reaction filter plate is prepared and applied according to the following method:

preparation and prefabrication of raw materials

Independently suspension-culturing Chlorococcus microalgae, Botryococcus, and Scenedesmus to obtain wastewater treatment algae suspension culture solution, centrifuging after entering a plateau phase, mixing at a wet weight ratio of 2:2:3, and re-suspending with pure water to obtain a suspension with an algae cell density of 6.35 × 10⁵The PVA powder is one/mL, the polymerization degree of pure PVA is 4000, and the alcoholysis degree is 88%.

Enriching and domesticating bacterial sludge of sewage treatment bacteria:

(A) adopting sterile initial culture solution to domesticate and enrich bacteria for sewage treatment, inoculating activated sludge into the culture solution according to the suspension solid concentration (MLSS) of mixed solution of 3.03g/L in a fermentation tank, stirring and culturing at 100rpm, and ensuring the culture conditions to be constant: the temperature is 17 ℃, the pH value is 7.5, and the dissolved oxygen is 3.0 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L; the initial culture solution also comprises 5g/L gel particles with the particle diameter of 3mm, the gel is 20 wt% of sodium alginate hydrogel, nitrobacteria and nitrosobacteria have the habit of attachment growth, the gel particles are increased to provide attachments, the proliferation activity of thalli is improved, thalli micelles are formed, the precipitation is convenient during liquid change, and the thalli flow is prevented.

(B) Culturing until MLSS reaches 8g/L, replacing acclimation culture solution every 8 hours by half, precipitating for 40min before replacing, removing supernatant, adding equal amount of sterile inorganic culture solution, and acclimating and culturing for 72 h; the concentrations of ammonium nitrogen and chemical oxygen demand in the domesticated culture solution are increased progressively along with the replacement times on the basis of the initial culture solution, and each time, the concentrations are increased progressively by 70 mg/L;

(C) and centrifuging after acclimatization and culture to obtain a precipitate, washing the precipitate with 10 times of normal saline for three times, discarding the supernatant, counting, identifying, and storing at 4 ℃ to obtain the bacterial sludge of the sewage treatment bacteria. Through culture and identification, the sewage treatment bacteria are mainly nitrobacteria, nitrosobacteria and denitrifying bacteria, and the thallus concentration of the nitrobacteria, the nitrosobacteria and the denitrifying bacteria in the bacterial sludge is 5.98 multiplied by 10⁷Per gram.

(1) heating the colorless transparent glass raw material to 800 ℃ for heat preservation, preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device after the colorless transparent glass raw material is completely melted, wherein the jet deposition process parameters are as follows: using 7.5MPa high-pressure argon as atomizing gas, setting the vertical spraying distance to be 30cm, setting the inner diameter of a liquid guide pipe to be 7mm, setting the spraying angle to be 52 degrees, horizontally placing a deposition disc, setting the horizontal moving speed of the deposition disc to be 3mm/s, setting the vertical downward moving speed to be 0.15mm/s, horizontally reciprocating the deposition disc at the same speed every 100s until the thickness of a deposition layer reaches 6cm, stopping deposition, immersing the deposition in cold water, and quickly cooling to obtain a deposition glass plate; the average diameter of the condensed glass particles is 0.75mm, pores are formed by stacking the glass particles, and the light transmittance of the deposited glass plate is 82%.

(2) Weighing 7 wt% of PVA, 3wt% of nano-silica, 2 wt% of diatomite, 2 wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃, keeping the temperature, slowly stirring and adding the nano-silica and the diatomite, uniformly stirring, ultrasonically degassing, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by using 1 XPBS, homogenizing, filtering by using single-layer gauze to obtain resuspended bacterial liquid, respectively centrifuging the resuspended bacterial liquid or algae culture suspension at 2500rpm for 10min, respectively taking bacterial sediment or algae sediment for storage at 4 ℃, mixing the bacterial sediment and the algae sediment according to a wet weight ratio of 10:1 to obtain a sewage treatment microorganism for fixation;

(4) mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 12:1, and magnetically stirring at 350rpm for 15 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing at 15kHz for 10 min; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering for 13min under the air pressure of 0.6 MPa;

(5) at 4 ℃, the catalyst contains 0.65wt percent of CaCl₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 1h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for solidification and crosslinking for 13h, the solidification and crosslinking are carried out, then the upflow type filtration and washing are carried out for 20min by using distilled water, the immobilized bioreaction filter plate is obtained, the immobilized bioreaction filter plate is placed in phosphate buffer solution at 4 ℃ and pH7.2 for standby, and the thickness of the surface film of the deposition glass PVA plate is measured to be 121 +/-6.6 mu m by adopting a Defelsko PositeTector 200C series ultrasonic coating thickness meter.

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, the ammonia nitrogen value is less than or equal to 200mg/L, one layer is arranged at 200-400 mg/L, two layers are arranged at 400-600 mg/L, and the rest is done in the same way. In the embodiment, the ammonia nitrogen value of the high ammonia nitrogen sewage is 558.9mg/L, and three layers of immobilized biological reaction filter plates are arranged.

(2) Aerating the high ammonia nitrogen sewage for 6 hours, then carrying out solid-liquid separation, filtering the liquid by adopting 25cm coarse sand, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized biological reaction filter plate on the liquid surface, maintaining the liquid surface height at 20cm, filtering the liquid layer by layer through the immobilized biological reaction filter plates, and keeping the hydraulic retention time of each layer of immobilized biological reaction filter plates at 0.7 hour;

(3) after the sewage liquid is injected, the fluorescent lamp is continuously illuminated for 24 hours, and each layer of the immobilized biological reaction filter plate is respectively illuminated with the illumination intensity of 1500 Lx.

Example 4: the immobilized biological reaction filter plate is prepared and applied according to the following method:

preparation and prefabrication of raw materials

Independently performing suspension culture on blue algae, diatom, spirulina and red bacteria to prepare sewage treatment algae suspension culture solution, centrifuging after entering a platform stage, mixing according to a wet weight ratio of 1:1:2:5, performing pure water resuspension, wherein the density of algae cells in the suspension is 4.11 multiplied by 10⁵one/mL.

The degree of polymerization of the PVA alone was 3000, and the degree of alcoholysis was 88%.

Enriching and domesticating bacterial sludge of sewage treatment bacteria:

(A) adopting sterile initial culture solution to domesticate and enrich bacteria for sewage treatment, inoculating activated sludge into the culture solution according to the mixed solution suspended solid concentration (MLSS) of 2.58g/L in a fermentation tank, stirring and culturing at 75rpm, and ensuring the culture conditions to be constant: the temperature is 16 ℃, the pH value is 7.3, and the dissolved oxygen is 2.5 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L; the initial culture solution also comprises 3.5g/L of gel particles, the particle size of the gel is 2mm, and the gel is 10 wt% of agar gel.

(B) Culturing until MLSS reaches 8g/L, replacing acclimation culture solution every 7 hours by half, precipitating for 30min before replacing, removing supernatant, adding equal amount of sterile inorganic culture solution, and acclimating and culturing for 60 h; the concentrations of ammonium nitrogen and chemical oxygen demand in the domestication culture solution are increased progressively along with the replacement times on the basis of the initial culture solution, and each time, the concentrations are increased progressively by 60 mg/L;

(C) and centrifuging after acclimatization and culture to obtain a precipitate, washing the precipitate with 10 times of normal saline for three times, discarding the supernatant, counting, identifying, and storing at 4 ℃ to obtain the bacterial sludge of the sewage treatment bacteria. Through culture and identification, the sewage treatment bacteria are mainly nitrifying bacteria, nitrosobacteria and denitrifying bacteria, and the thallus concentration of the nitrifying and/or denitrifying bacteria in the bacterial sludge is 3.89 multiplied by 10⁷Per gram.

(1) heating the colorless transparent glass raw material to 850 ℃ for heat preservation, preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device after the colorless transparent glass raw material is completely melted, wherein the jet deposition process parameters are as follows: using 7.5MPa high-pressure argon as atomizing gas, setting the vertical spraying distance to be 30cm, setting the inner diameter of a liquid guide pipe to be 8mm, setting the spraying angle to be 60 degrees, horizontally placing a deposition disc, setting the horizontal moving speed of the deposition disc to be 4mm/s, setting the vertical downward moving speed to be 0.2mm/s, horizontally reciprocating the deposition disc at the same speed every 100s until the thickness of a deposition layer reaches 8cm, stopping deposition, immersing the deposition in cold water, and quickly cooling to obtain a deposition glass plate; the average diameter of the condensed glass particles was 0.9mm, pores were formed by stacking the glass particles, and the light transmittance of the deposited glass sheet was 88%.

(2) Weighing 7.5 wt% of PVA, 3.5 wt% of nano-silica, 1 wt% of diatomite, 2 wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃, preserving heat, slowly stirring and adding the nano-silica and the diatomite, ultrasonically degassing after uniformly stirring, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by using 1 XPBS, homogenizing, filtering by using single-layer gauze to obtain resuspended bacterial liquid, respectively centrifuging the resuspended bacterial liquid or algae culture suspension at 2500rpm for 10min, respectively taking bacterial sediment or algae sediment, storing at 4 ℃, mixing the bacterial sediment and the algae sediment according to a wet weight ratio of 1:1, and taking the mixture as the sewage treatment microorganism for fixation.

(4) Mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 10:1, and magnetically stirring at 400rpm for 12 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing at 15kHz for 10 min; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering with the wind pressure of 0.5MPa for 18 min;

(5) at 4 ℃, the catalyst contains 0.7 wt% of CaCl₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 1.2h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for curing and crosslinking for 14h, after curing and crosslinking, the immobilization and crosslinking are filtered and washed by distilled water in an upflow type manner for 25min, thus obtaining an immobilization biological reaction filter plate, the immobilization biological reaction filter plate is placed in phosphate buffer solution at 4 ℃ and pH7.2 for standby, and the thickness of PVA film on the surface of the deposition glass plate is measured to be 133 +/-6.9 mu m by adopting a Defelsk PositeTector 200C series ultrasonic coating thickness meter.

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, the ammonia nitrogen value is less than or equal to 200mg/L, one layer is arranged at 200-400 mg/L, two layers are arranged at 400-600 mg/L, and the rest is done in the same way. In the embodiment, the ammonia nitrogen value of the high ammonia nitrogen sewage is 615.2mg/L, and four layers of immobilized biological reaction filter plates are arranged.

(2) Aerating the high ammonia nitrogen sewage for 4 hours, then carrying out solid-liquid separation, filtering the liquid by adopting coarse sand of 20-30 cm, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized biological reaction filter plate on the liquid surface, maintaining the liquid surface height at 10-30 cm, filtering the liquid layer by layer through the immobilized biological reaction filter plates, and keeping the hydraulic retention time of each layer of immobilized biological reaction filter plates at 0.6 hour;

(3) after the sewage liquid is injected, the fluorescent lamp is continuously illuminated for 24 hours, and the illumination intensity is 2500 Lx;

Example 5: the immobilized biological reaction filter plate is prepared and applied according to the following method:

preparation and prefabrication of raw materials

Separately suspension culturing Chlorella and red bacteria to obtain suspension culture solution, centrifuging after entering a plateau phase, mixing at a wet weight ratio of 1:3, and resuspending with pure water to obtain suspension culture solution with algae cell density of 5.29 × 10⁵one/mL.

The degree of polymerization and alcoholysis of the PVA alone was 5000%.

Enriching and domesticating bacterial sludge of sewage treatment bacteria:

(A) adopting sterile initial culture solution to domesticate and enrich bacteria for sewage treatment, inoculating activated sludge into the culture solution according to the mixed solution suspended solid concentration (MLSS) of 2.33g/L in a fermentation tank, stirring and culturing at 75rpm, and ensuring the culture conditions to be constant: the temperature is 15 ℃, the pH value is 7.4, and the dissolved oxygen is 2.2 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L; the initial culture solution also comprises 4g/L of gel particles, the particle size of the gel is 2mm, and the gel is 1.5 wt% of agarose gel.

(B) Culturing until MLSS reaches 8g/L, replacing acclimation culture solution every 7 hours by half, precipitating for 25min before replacing, removing supernatant, adding equal amount of sterile inorganic culture solution, and acclimating and culturing for 70 h; the concentrations of ammonium nitrogen and chemical oxygen demand in the domesticated culture solution are increased progressively along with the replacement times on the basis of the initial culture solution, and the concentrations are increased by 65mg/L each time;

(C) centrifuging to obtain precipitate after acclimatization culture, washing the precipitate with 10 times of normal saline for three times, discarding supernatant, counting, identifying, and storing at 4 deg.C to obtain the final productWater treatment of bacterial sludge. Through culture and identification, the sewage treatment bacteria are mainly nitrobacteria, nitrosobacteria and denitrifying bacteria, and the total thallus concentration of the nitrobacteria, the nitrosobacteria and the denitrifying bacteria in the bacterial sludge is 4.42 multiplied by 10⁷Per gram.

(1) heating glass raw materials to 900 ℃, preserving heat, preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device after the glass raw materials are completely melted, wherein the jet deposition process parameters are as follows: using 9MPa high-pressure argon as atomizing gas, setting the vertical spraying distance to be 35cm, setting the inner diameter of a liquid guide pipe to be 7mm, setting the spraying angle to be 55 degrees, horizontally placing a deposition disc, setting the horizontal moving speed of the deposition disc to be 3mm/s, setting the vertical downward moving speed to be 0.15mm/s, horizontally reciprocating the deposition disc at the same speed every 100s until the thickness of a deposition layer reaches 9cm, stopping deposition, immersing the deposition in cold water, and quickly cooling to obtain a deposition glass plate; the average particle size of the condensed glass particles was 0.8mm, pores were formed by stacking the glass particles, and the light transmittance of the deposited glass plate was 81%.

(2) Weighing 7 wt% of PVA, 2 wt% of nano-silica, 1 wt% of diatomite, 1.5 wt% of sodium alginate and the balance of water according to mass fraction, adding pure PVA and sodium alginate powder into pure water, heating in a water bath at 95 ℃ until the PVA and the sodium alginate are completely dissolved, cooling to 35 ℃, keeping the temperature, slowly stirring and adding the nano-silica and the diatomite, ultrasonically degassing after uniformly stirring, and then cooling to room temperature to obtain a PVA solution;

(3) resuspending bacterial sludge containing sewage treatment bacteria by using 1 XPBS, homogenizing, filtering by using single-layer gauze to obtain resuspended bacterial liquid, respectively centrifuging the resuspended bacterial liquid or algae culture suspension at 2500rpm for 10min, respectively taking bacterial precipitates or algae precipitates for storage at 4 ℃, and mixing the bacterial precipitates and the algae precipitates according to a wet weight ratio of 6:1 to obtain the sewage treatment microorganism for fixation.

(4) Mixing the PVA solution cooled to room temperature with the sewage treatment microorganisms according to the weight ratio of 15:1, and magnetically stirring at 250rpm for 15 min; immediately and completely immersing the deposited glass plate into the PVA mixed solution, and ultrasonically degassing at 18kHz for 11 min; taking out the deposited glass plate, sealing and installing the glass plate at the outlet of the stainless steel air duct, and removing the redundant PVA mixed solution in the pores by air showering with the air pressure of 0.47MPa for 18 min;

(5) at 4 ℃, the catalyst contains 0.6wt percent of CaCl₂The saturated boric acid solution is filtered through an upflow type deposition glass plate after air showering, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 0.8h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for curing and crosslinking for 12h, after curing and crosslinking, the immobilization and crosslinking are filtered and washed by distilled water in an upflow type manner for 20min, thus obtaining an immobilization biological reaction filter plate, the immobilization biological reaction filter plate is placed in phosphate buffer solution at 4 ℃ and pH7.2 for standby, and the thickness of PVA film on the surface of the deposition glass plate is measured to be 129 +/-3.8 mu m by adopting a Defelsk PositeTector 200C series ultrasonic coating thickness meter.

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, the ammonia nitrogen value is less than or equal to 200mg/L and is provided with one layer, 200-400 mg/L and two layers, 400-600 mg/L and three layers, 600-800 mg/L and four layers, and the like. In the embodiment, the ammonia nitrogen value of the high ammonia nitrogen sewage is 789.7mg/L, and four layers of immobilized biological reaction filter plates are arranged.

(2) Aerating the high ammonia nitrogen sewage for 3 hours, then carrying out solid-liquid separation, filtering the liquid by adopting 28cm coarse sand, then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, completely immersing the upper surface of each layer of immobilized biological reaction filter plate on the liquid surface, maintaining the liquid surface height at 25cm, filtering the liquid layer by layer through the immobilized biological reaction filter plates, and keeping the hydraulic retention time of each layer of immobilized biological reaction filter plates at 0.8 hour;

(3) after the sewage liquid is injected, the fluorescent lamp is continuously illuminated for 24 hours, and each layer of the immobilized biological reaction filter plate is respectively illuminated with the illumination intensity of 1750 Lx.

Example 6: the rest of the procedures were the same as those in example 4 except that the initial culture solution further included 3g/L of gel particles having a particle size of 3mm, and the gel was a mixture of carbomer gel, xanthan gum and polyacrylamide gel, which contained 20 wt% of carbomer gel, 25 wt% of xanthan gum and 55 wt% of polyacrylamide gel. The carbomer gel concentration is 30%, the xanthan gum concentration is 15% and the polyacrylamide gel concentration is 25%, the carbomer gel, the xanthan gum and the polyacrylamide gel are all prepared by pure water, and the carbomer gel, the xanthan gum and the polyacrylamide gel are proportioned, mixed and crushed into gel particles with the average particle size of 3mm after solidification.

Comparative example 1: glass plates immobilized with ammonia oxidizing bacteria were prepared according to the method disclosed in chinese patent CN108164000A as a subsequent control group.

Comparative example 2: anaerobic ammonia oxidizing bacteria immobilized fixed bioactive filler based on a reticular carrier is prepared according to the method disclosed in Chinese patent CN103951048A and is used as a subsequent control group.

Comparative example 3: the rest was the same as example 5 except that no sewage-treating microorganism was added to the PVA film.

To test the performance of the present invention, the following test experiments were performed:

1. and (3) detecting the immobilized biological reaction filter plate by using an SEM (scanning electron microscope).

SEM scanning and shooting are carried out on the immobilized biological reaction filter plate prepared in the example 1, and the result is shown in figure 1.

As can be seen from fig. 1, the deposited glass sheet is formed by loosely stacking a plurality of small glass droplet solidified bodies, and the spray deposition process causes the glass droplets to adhere to each other before solidification, and then to solidify rapidly, stacking each other to generate pores, thereby forming a porous glass sheet.

PVA with high polymerization degree has larger viscosity, and after the excess PVA solution is removed by air shower, a uniform film layer is formed after wall hanging, and the pores of the deposited glass plate are not blocked.

2. Pore size distribution of deposited glass sheets

The deposited glass plates prepared in examples 1 to 5 were used as samples, and the pore size distribution of the samples was measured using an ASAP2010 or 2020 analyzer, and the results are shown in table 1:

TABLE 1 pore size distribution in the samples

Group of	Pore size Range (μm)
		Example 1	149～337
Example 2	413～674
		Example 3	333～542
Example 4	321～559
		Example 5	298～422

3. BET pore size analysis

The deposited glass plates prepared in examples 1 to 5 were used as samples, and comparative example 2 was used as a filler to prepare a reaction bed having a thickness of 30cm, and the specific surface area and the ratio of pore volume were analyzed by the BET method, and the results are shown in table 2:

TABLE 2 BET pore size analysis results

S_{General assembly}: total ratio tableArea; v_{General assembly}: total pore volume;

as can be seen by combining the data in tables 1 and 2, the deposited glass plate has a large number of pores, so that the specific surface area and the pore volume are large, and the deposited glass plate can adsorb and fix a large number of PVA membranes containing microorganisms, and simultaneously, the contact reaction area between the substrate filter plate and the microorganisms is increased, and the utilization rate and the reaction efficiency of the microorganisms are improved. In contrast, comparative examples 1 and 2, which are solid carriers, have a very small specific surface area per unit volume, and have very limited microorganisms adsorbed and immobilized, which cannot be compared with the present invention. Comparative example 2 even when the reaction bed was formed as a packing, the specific surface area was significantly lower than that of the porous deposited glass plate.

4. Detection of ammonia nitrogen removal rate of high ammonia nitrogen sewage

A reaction bed with a thickness of 10cm was prepared by using comparative example 2 as a packing, and 1m was treated by the sewage treatment method provided in examples 1 to 5 and comparative examples 1 to 3³And (3) taking the treated high ammonia nitrogen sewage with corresponding concentration, determining ammonia nitrogen content and COD, and calculating the removal rate of ammonium nitrogen:

ammonium nitrogen removal (%) - (influent ammonia nitrogen content-effluent ammonia nitrogen content)/influent ammonia nitrogen content 100%

The results are shown in Table 3

TABLE 3 detection of Ammonia Nitrogen removal Activity of immobilized bioreaction Filter plates

The results in table 3 show that the ammonia nitrogen removal rate in examples 1 to 5 is significantly higher than that in comparative examples 1 to 3 and the chemical oxygen demand is significantly reduced under the condition of a short Hydraulic Retention Time (HRT), which indicates that the present invention can efficiently treat high ammonia nitrogen wastewater. The contrast example 3 does not contain sewage treatment microorganisms, and the comparison with the example 5 shows that the sewage treatment mainly depends on active sewage treatment microorganisms fixed in a PVA film, carrier materials such as PVA, sodium alginate and diatomite hardly have ammonia nitrogen removal effect under the condition of not containing the sewage treatment microorganisms, the effective contact and treatment area is small due to the fact that the microorganisms are loaded on the surface of the solid glass plate, ammonia nitrogen cannot be removed in a short time, and the packed bed formed in the contrast example 2 is fixed with water-free treatment microorganisms, but the treatment efficiency is remarkably limited by the mass transfer performance of a high molecular carrier, and meanwhile, the specific surface area is small, so that the treatment efficiency is remarkably lower than that of the examples 1-5. When the bacteria and the algae are contained at the same time, the treatment effect is better.

The ammonia nitrogen removal rates of the sewage treatment methods of examples 1 and 5 and comparative examples 1 to 3 were measured according to the above-mentioned methods at different hydraulic retention times, and the results are shown in Table 4.

TABLE 4 Effect of hydraulic retention time on Ammonia Nitrogen removal

The hydraulic retention time reflects the reaction time of microorganisms and anhydrous water, the optimal hydraulic retention time of the embodiments 1 and 5 is 1-1.5 h, the removal rate of ammonia nitrogen is not greatly improved after the optimal hydraulic retention time is prolonged, which indicates that the maximum treatment capacity of the filter plate is stably reached within 1-1.5 h, the optimal hydraulic retention time of the comparison examples 1-3 is about 3h, the maximum removal rate of ammonia nitrogen is obviously lower than that of the embodiments 1 and 5, which indicates that the maximum sewage treatment load of the comparison examples 1-3 is reached within 3h, and the treatment effect is obviously lower than that of the embodiments 1 and 5.

The control example 1 has limited surface area, less supported microorganisms and smaller contact area with sewage, so the ammonia nitrogen removal rate under the maximum load cannot exceed 10%, the control example 2 has lower biological reaction rate due to limited mass transfer performance and material thickness, so the ammonia nitrogen removal rate under full load is lower than 60%, and the control example 3 has no supported microorganisms, so the ammonia nitrogen removal effect mainly depends on the adsorption effect of large-area PVA film materials on ammonia nitrogen, and the ammonia nitrogen can be regurgitated after long-time treatment, so the ammonia nitrogen removal rate is reduced after exceeding 3 h.

4. Mass transfer Performance test

The PVA mixed solution containing the microorganisms in the embodiments 1 to 5 or the PVA solution containing no microorganisms in the comparative embodiment 3 is coated on the surface of a solid glass plate, a PVA film with the same thickness as that of the deposited glass plate is formed through crosslinking treatment, and the PVA film is soaked in PBS to be used as a sample for subsequent effective mass transfer coefficient determination. The PVA mixture in example 5 was coated to form a 1mm PVA film as a control sample.

According to the literature: determination of matrix diffusion coefficient in Guanqingkun, Poplar and PVA gel and optimization of mass transfer performance [ J ] environmental engineering report, 2017(3) determination method of mass transfer coefficient in the embodiments 1-5 and the comparative embodiments 2-3 determine effective mass transfer coefficient of PVA film or mesh material.

The results are shown in Table 4:

TABLE 5 effective Mass transfer coefficient of PVA film or Web Material

Comparison between comparative example 3 and example 5 in table 5 shows that the mass transfer coefficient of the PVA membrane is slightly affected by the addition of the microorganisms, the mass transfer performance of the carrier material is not affected, the substrate and the product can freely enter and exit the carrier, and the limitation effect of poor mass transfer performance of the PVA polymer material on the microbial reaction is overcome. Although mass transfer performance can be improved by making the film layer thin, in practical use, the PVA films used alone in the film thicknesses of examples 1 to 5 have extremely poor mechanical properties and are easy to break and break, so that a deposited glass plate is required to support load.

The mass transfer coefficients of the embodiments 1 to 5 are not changed greatly under the condition of a film thickness of 60 to 140 microns, and the mass transfer performance is stable, but when the film thickness is increased to 1mm, the mass transfer performance is greatly reduced, which shows that the film thickness has a large influence on the mass transfer performance, and when the film layer is thick, the bidirectional diffusion of substrates and products is hindered, so that the biological reaction rate is limited. Comparison of data in example 5 and comparative example 2 shows that, in the same millimeter-scale condition, the mass transfer performance of the PVA carrier in the present invention is also significantly better than that of the comparative mesh material, which indicates that the addition of sodium alginate and diatomaceous earth also contributes to the mass transfer performance of the polymer carrier.

In conclusion, the porous deposition glass plate formed after glass droplet spraying, cooling and depositing is used as a supporting carrier, the specific surface area is large under the same volume, the contact area between the loaded PVA film and substrate liquid is large, microorganisms are fixed in the PVA film layer, the bioavailability is greatly improved, and the treatment efficiency is improved. The pore size of the deposited glass plate is moderate, the fluidity of the infiltration filtration and the hydraulic retention time are considered, and the treatment time of the substrate in unit volume is reduced while the ammonia nitrogen elimination rate is ensured. The glass material texture is hard at normal temperature for need not consider the mechanical strength of embedding carrier behind the load PVA membrane, adopt the PVA of high polymerization degree as embedding material, viscosity is high, and the cohesiveness is strong, can be able to bear or endure to erode behind the formation PVA membrane, is difficult for droing, adds ductility and the mechanical strength that can show increase PVA membrane after the modification of nanometer silica, prevents that PVA membrane from tearing. PVA has good film forming property, a PVA film layer loaded on the surface of a deposition glass plate is thin, and the defect of poor mass transfer property of a PVA material is overcome by adding sodium alginate; sodium alginate and diatomite are added into the PVA film as adsorption and fixation components to increase the fixation amount of microorganisms, the microorganism fixation effect is stable, the loss is not easy, the fixation has little influence on the activity of the microorganisms, and the high activity of the microorganisms can be maintained for a long time. When the immobilized biological reaction filter plate is applied to sewage treatment, the number of the filter plate layers can be flexibly regulated according to the ammonia nitrogen level of sewage, the treatment strength is changed, unnecessary waste is reduced, high-ammonia nitrogen sewage is efficiently treated, and the treatment cost is reduced. By gradually increasing the ammonia nitrogen load level of the sewage treatment bacteria, the anhydrous treatment bacteria are gradually domesticated and enriched, the ammonia nitrogen conversion activity of the bacteria is improved while the number of the bacteria is increased, and the high-activity sewage treatment bacteria are obtained. When the bacteria are mainly nitrifying or nitrosating bacteria, aerobic nitrification or nitrosating reaction is mainly carried out, oxygen can be provided for the nitrification or nitrosating reaction due to aeration and co-embedding of the algae, the nitrification or nitrosating reaction rate is improved, meanwhile, the algae can also fix ammonia nitrogen and phosphorus to carry out sewage purification, the hydraulic retention time can be reduced under the double purification treatment of the algae and the bacteria, and the sewage treatment efficiency is obviously improved. When the anaerobic condition is adopted, the activity of denitrifying bacteria is improved, and sewage treatment can be carried out under the condition of non-aeration operation and algae.

The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.

Claims

1. An immobilized biological reaction filter plate, which is characterized in that: contain deposit glass board and sewage treatment microorganism, the deposit glass board is formed by the deposit bonding behind the glass molten drop rapid condensation, and condensation glass granule average particle diameter is 0.4~1.1mm, piles up between the glass granule and forms the hole, and the aperture scope of hole is 149~674 mu m, the thickness of deposit glass board is 1~10cm, and the even load of deposit glass inboard, surface has one deck PVA film, the thickness of PVA film is 56~163 mu m, and the PVA film internal fixation has the sewage treatment microorganism, the sewage treatment microorganism is sewage treatment bacterium and/or sewage treatment alga.

2. An immobilized biological reaction filter plate according to claim 1, wherein: the sewage treatment bacteria are nitrifying bacteria, nitrosobacteria, rhodobacter and denitrifying bacteria, the sewage treatment algae comprise chlorella, one or more of blue algae, diatom, spirulina, chlorella, botryococcus and scenedesmus, the light transmittance of the deposition glass plate is 75-90%, the polymerization degree of PVA is 2000-6000, and the alcoholysis degree is 87-89%.

3. The method for preparing the immobilized biological reaction filter plate according to claim 1 or 2, comprising the following steps:

(1) heating the glass raw materials to 700-950 ℃, preserving heat, completely melting, and preparing the liquid glass into a deposited glass plate by adopting a multilayer jet deposition plate preparation device, wherein the jet deposition process parameters are as follows: taking 5-10 MPa high-pressure argon as atomizing gas, wherein the vertical spraying distance is 25-35cm, the inner diameter of a liquid guide pipe is 6-8 mm, the spraying angle is 45-60 degrees, a deposition disc is horizontally placed, the horizontal moving speed of the deposition disc is 2-4 mm/s, the vertical moving speed is 0.1-0.2 mm/s, the deposition disc horizontally reciprocates at the same speed every 100s until the thickness of the deposition layer reaches 1-10 cm, the deposition is stopped, and the deposition is immersed in cold water and rapidly cooled to obtain a deposition glass plate;

(5) at the temperature of 4 ℃, the CaCl with the content of 0.5 to 0.8wt percent is added₂The saturated boric acid solution is filtered through the deposition glass plate after air showering in an up-flow mode, the saturated boric acid solution completely immerses the whole volume of the deposition glass plate, the filtering time is 0.5-1.5 h, the deposition glass plate is taken out and placed in a refrigerator at 4 ℃ for curing and crosslinking for 10-16 h, and the evaporation is used for curing and crosslinkingAnd (3) filtering and washing the distilled water in an upflow manner for 15-25 min to obtain an immobilized biological reaction filter plate, and placing the immobilized biological reaction filter plate in a phosphate buffer solution with the temperature of 4 ℃ and the pH value of 7.2 for storage and standby.

4. The method for preparing an immobilized bioreaction filter plate according to claim 3, wherein the method comprises the following steps: the total concentration of the nitrifying bacteria, the nitrosobacteria and the denitrifying bacteria in the bacterial sludge containing the sewage treatment bacteria is 1.56-5.98 multiplied by 10⁷The cell density of algae in the algae culture suspension is 1.22-6.35 multiplied by 10⁵Per mL; when the fixing sewage treatment microorganisms comprise thallus precipitates and algae precipitates, the wet weight ratio of the thallus precipitates to the algae precipitates is 1-10: 1.

5. The method for preparing an immobilized bioreaction filter plate according to claim 3, wherein the method comprises the following steps: the step (1) also comprises a bacterial sludge enrichment and domestication step of the sewage treatment bacteria, which comprises the following steps:

(A) domesticating and enriching sewage treatment bacteria by adopting sterile initial culture solution, inoculating activated sludge into the culture solution according to the MLSS of 2.19-3.03 g/L in a fermentation tank, and stirring and culturing at 50-100 rpm to ensure that the culture conditions are constant: the temperature is 14-17 ℃, the pH = 7.0-7.5, and the dissolved oxygen is 2.0-3.0 mg/L; the concentration of ammonium nitrogen in the initial culture solution is 250mg/L, and the chemical oxygen demand is 100 mg/L;

6. The method for preparing an immobilized bioreaction filter plate according to claim 5, wherein the method comprises the following steps: the initial culture solution further comprises 2-5 g/L of gel particles, the particle size of the gel particles is 1-3 mm, and the gel is one or more of sodium alginate gel, agar gel, carbomer gel, xanthan gum, agarose gel and polyacrylamide gel.

7. A method for treating ammonia nitrogen sewage by using the immobilized biological reaction filter plate in claim 1 or 2 is characterized by comprising the following specific steps:

(1) polishing the side surface of an immobilized biological reaction filter plate, then sealing and installing the side surface of the immobilized biological reaction filter plate in a completely transparent sewage treatment reactor, vertically arranging the immobilized biological reaction filter plates at equal intervals, pre-installing 1 XPBS (phosphate buffer solution) in an up-flow manner, and keeping each layer of immobilized biological reaction filter plate completely immersed; the sewage treatment bacteria fixed in the immobilized biological reaction filter plate comprise nitrifying bacteria and nitrosobacteria;

(2) performing solid-liquid separation on the ammonia nitrogen sewage, filtering the liquid by coarse sand of 20-30 cm, and then injecting the filtered liquid into a sewage treatment reactor in an up-flow manner, wherein the liquid level completely submerges the upper surface of each layer of immobilized biological reaction filter plate, the liquid level height is maintained at 10-30 cm, the liquid is filtered through the immobilized biological reaction filter plates layer by layer, and the hydraulic retention time of each layer of immobilized biological reaction filter plate is 0.3-1 h;

8. The method for treating ammonia nitrogen sewage by using the immobilized biological reaction filter plate in claim 7 is characterized by comprising the following steps: the number of the layers of the immobilized biological reaction filter plate is in direct proportion to the ammonia nitrogen value, one layer is arranged at the ammonia nitrogen value of less than or equal to 200mg/L, two layers are arranged at 200-400 mg/L, three layers are arranged at 400-600 mg/L, and the rest is done in the same way; carrying out aeration operation before solid-liquid separation of the ammonia nitrogen sewage; and (3) respectively illuminating each layer of the immobilized biological reaction filter plate in the step (3), wherein the illumination intensity is 1500 Lx.