CN110452901A - A kind of immobilization biological reaction filter plate and its preparation method and application - Google Patents
A kind of immobilization biological reaction filter plate and its preparation method and application Download PDFInfo
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- CN110452901A CN110452901A CN201910755332.3A CN201910755332A CN110452901A CN 110452901 A CN110452901 A CN 110452901A CN 201910755332 A CN201910755332 A CN 201910755332A CN 110452901 A CN110452901 A CN 110452901A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
- C02F3/325—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae as symbiotic combination of algae and bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/36—Adaptation or attenuation of cells
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a kind of immobilization biological reaction filter plates and its preparation method and application, it includes deposited glass and microorganism that immobilization biological, which reacts filter plate, using the porous deposited glass formed after glass molten drop spray cooling deposition as support carrier, large specific surface area under same volume, it is also larger with the contact area of substrate liquid after load PVA film, microorganism is fixed in PVA film layer, and bioavilability is substantially improved, and promotes treatment effeciency.The pore size of deposited glass is moderate, takes into account the mobility and hydraulic detention time of permeation filtration, and the processing time of unit volume substrate is reduced while guaranteeing ammonia nitrogen elimination factor.Modified PVA film microorganism fixed effect is stablized, and minimum to the activity influence of microorganism.When immobilization biological reacts filter plate applied to sewage treatment, processing intensity can be changed according to the ammonia nitrogen level flexible modulation filter plate number of plies of sewage, reduce unnecessary waste, efficient process high-ammonia-nitrogen sewage reduces processing cost.
Description
Technical field
The present invention relates to immobilized microorganism field, in particular to a kind of immobilization biological reaction filter plate and preparation method thereof
And application.
Background technique
Microorganism technique for fixing refer to physics or chemistry method, by superior microorganism it is highdensity be fixed on it is specific
Carrier on and within the regular hour be able to maintain activity, can also meet the biology of specified requirement under suitable growth conditions
Technique for fixing.The basic point of departure of microorganism technique for fixing is, treatment process is improved based on superior microorganism population
High efficiency and stability improve microbe density in unit volume, eliminate the losing issue of microorganism.Compare traditional active sludge
Method microbial biomass is low, easily there is sludge bulking and loss, it is poor to waste water quality water adaptability the problems such as, this microorganism is solid
The processing for determining technology for stain disease has fairly obvious advantage:
(1) superior microorganism high density is fixed in a certain space, greatly improves micro- life in bioreactor
Object concentration is conducive to the speed for improving reaction, reduces the time of reaction and then reduces the occupied area and volume for the treatment of facility.
(2) mixing of nitrifier common in biological denitrificaion and denitrifying bacterium can be embedded, is realized in same reactor while fixed
The target of different types of microorganisms.(3) microorganism is fixed on a certain carrier inside, is conducive to improve microorganism to ambient enviroment change
The adaptability of change increases reactor and resists the ability of impact load in stain disease treatment process and to the resistance to of noxious material
Stress.(4) separation of solid and liquid can be realized rapidly after the reaction by fixed microorganism and surplus sludge volume is few.5. stability is strong,
Treatment effeciency is high, can purify and keep high-efficiency strain.
Currently, immobilized microorganism preparation method has very much, any one can be limited in microorganism in certain space
And certain active technology is kept to can be used for preparing immobilized dominant microorganism.In general the preparation side of immobilized microorganism
Method has several: investment, absorption method, cross-linking method, covalent coupling method.Absorption method mostly uses the porous materials physics such as diatomite
Absorption microorganism is fixed, and binding force is weak, and due to not being chemically treated, microbial activity is high;Cross-linking method is to utilize friendship
The groups covalent bonds such as amino, hydroxyl, the sulfydryl of connection agent and antimicrobial surface are crosslinked, and connected networking between microbial cells is made
Shape structure, but this method chemical reaction is fierce, and crosslinking agent is more toxic, and microbial activity loss is larger.Covalent coupling method is
It is keyed with chemistry by micro- life using microbial cell surface functional group (such as amino, carboxyl, sulfydryl) and carrier surface group
The fixed method of object, therefore be tightly combined, stability is good, but reaction is acutely, complicated for operation, difficult to control when group combination, fixed
Microbial activity afterwards is lower.And investment uses carrier imbedded microbe, reacts soft, and the immobilized spherule prepared is mechanical
Intensity is high, and the bond strength of carrier and microorganism is moderate, and it is that current immobilized microorganism field is most-often used that microbial activity is high
A kind of method.
Carrier for microorganism embedded immobilization can substantially be divided into two major classes: one kind is that natural polymer gel carries
Body, such as agar, carrageenan, sodium alginate etc.;Natural high-molecular gel carrier is mainly using sodium alginate as representative
More extensive microbial fixed carrier is applied at present.It is extracted from natural seaweed, and it is right under normal circumstances to the advantage is that
Biology does not have toxicity, and mass-transfer performance is good, and price is lower, and disadvantage is that intensity is slightly lower, is not suitable for using in the case of high aeration, detest
It is easy to be decomposed under oxygen.Another kind of is organic polymer gel carrier, such as PVA, poly- alum, silica gel etc., wherein most with PVA
It is representative.Compared with natural polymer gel carrier, immobilization particle mechanical strength that organic polymer gel carrier is made into
It is big compared with the immobilization particle that natural polymer gel carrier is made into, but its mass-transfer performance is made into not as good as natural polymer gel carrier
Immobilization particle, and embed after to microorganism activity it is also larger, easily cause and be fixed microbial inactivation.
In addition to this, traditional embedded immobilization microbial is mostly porous small ball preparation, and specific surface area is smaller, with connecing for substrate
Contacting surface product is smaller, and microorganism more is embedded and is fixed on inside macromolecule carrier, treatment effect strong depend-ence or is limited to carrier
Mass-transfer performance, and macromolecule carrier solidifies that the embedding ball mass-transfer performance being cross-linked to form is poor, and microbiological treatment efficiency can not be most
Bigization.Meanwhile needing a large amount of immobilized microorganism preparation as filler when unit volume substrate solution continuous processing, waterpower is stopped
Stay the time larger, treatment effect is slower, and efficiency is lower.
Summary of the invention
The technical problems to be solved by the invention: for more present in current immobilized microorganism preparation and preparation process
Kind defect, the present invention provides a kind of immobilization biological reaction filter plate, using porous deposited glass as support carrier, increase
With substrate contact area, high mechanical strength, surfaces externally and internally attachment is fixed with microorganism, and when carrying out successive reaction, microorganism is utilized
Rate is high, and mass-transfer performance is excellent, and treatment effeciency is high.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of immobilization biological reaction filter plate, includes deposited glass and sewage treatment microorganism, the deposited glass
It is bonded by being deposited after glass molten drop rapid condensation, anti-condensation glass mean particle size is 0.4~1.1mm, between glass particle
Accumulation forms hole, and hole pore diameter range is 149~674 μm, the deposited glass with a thickness of 1~10cm, deposit glass
Plate inner and outer surfaces uniform load has one layer of PVA film, the PVA film with a thickness of 56~163 μm, be fixed at sewage in PVA film
Manage bacterium and/or sewage treatment algae.
Preferably, the sewage treatment bacterium is nitrobacteria, nitrite bacteria and denitrifying bacteria, the sewage treatment
Algae includes chlorella, one of cyanobacteria, diatom, spirulina, red bacterium, Nannochloropsis oculata, Wild Vitis species, scenedesmus or a variety of, institute
The light transmittance for stating deposited glass is 75~90%, and the degree of polymerization of the PVA is 2000~6000, alcoholysis degree 87~89%.
A kind of preparation method of above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) glass raw material is heated to 700~950 DEG C of heat preservations, liquid glass is sunk using multilayer spray after being completely melt
Product plate preparation facilities prepares deposited glass, spray deposition technology parameter are as follows: using 5~10MPa high pressure argon gas as atomization gas
Body, vertical spray distance are 25-35cm, and drain bore is 6~8mm, and spray angle is 45 °~60 °, and sediment pan level is put
It sets, sediment pan horizontal movement velocity is 2~4mm/s, and vertically moving down speed is 0.1~0.2mm/s, and sediment pan is every 100s with phase
Make horizontal back and forth movement with speed, until deposit thickness stops deposition when reaching 1~10cm, deposit is immersed fast in cold water
Prompt drop temperature obtains deposited glass;
(2) 6~8wt%PVA is weighed by mass fraction, 2~4wt% nano silica, 1~3wt% diatomite, 1~
3wt% sodium alginate, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths to PVA, seaweed
Sour sodium is completely dissolved, and is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, ultrasonic after mixing evenly
Degasification is then cooled to room temperature and obtains PVA solution;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, bacterial sediment and/or algae precipitating is used into sewage treatment microorganism as fixed;
(4) will be cooled to 250 after the PVA solution of room temperature is mixed with sewage treatment microorganism by weight 4~20:1~
10~20min of 500rpm magnetic agitation;Deposited glass is completely immersed in PVA mixed liquor immediately, 10~20kHz ultrasound degasification
5~15min;Deposited glass is taken out, stainless steel ducting outlet is seal-installed on, 0.4~0.8MPa wind pressure wind drenches 5~20min
Remove PVA mixed solution extra in hole;
At (5) 4 DEG C, 0.5~0.8wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after
Deposited glass, the saturation boric acid solution is totally submerged entire deposit glass plate bulk, and 0.5~1.5h of filtration time takes
Deposited glass is placed in 10~16h of solidification crosslinking in 4 DEG C of refrigerator out, with distilled water up flow type filtration washing 15 after solidification crosslinking
~25min reacts filter plate to get immobilization biological, and immobilization biological reaction filter plate is placed in 4 DEG C, and the phosphate of pH7.2 is slow
It is saved backup in fliud flushing.
Preferably, nitrobacteria in the bacterium mud of the bacterium containing sewage treatment, nitrite bacteria and denitrifying bacteria bacterium
Body total concentration is 1.56~5.98 × 107A/g, algae cell density is 1.22~6.35 × 10 in the algae culture suspension5
A/mL;When the fixation includes bacterial sediment and algae precipitating with sewage treatment microorganism, bacterial sediment precipitates wet with algae
Again than for 1~10:1.
Preferably, the step (1) further includes the bacterium mud acclimating step of sewage treatment bacterium, specific as follows:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, it in the fermenter will be active dirty
Mud is that 2.19~3.03g/L accesses 50~100rpm stir culture in culture solution by MLSS, guarantees that condition of culture is constant: temperature
14-17 DEG C, pH=7.0~7.5, dissolved oxygen 2.0-3.0mg/L;Ammonium nitrogen concentration is 250mg/L, chemistry in the initial incubation liquid
Oxygen demand is 100mg/L;
(B) culture solution is tamed in the replacement of every 6~8 hours half amounts after culture reaches 8g/L to MLSS, change before liquid and first precipitate 20~
Then 40min removes supernatant and the sterile minimal media liquid of equivalent is added, altogether 48~72h of domestication culture;In the domestication culture solution
Ammonium nitrogen and COD concentration are incremented by the basis of initial incubation liquid with replacement number, are incremented by 50~70mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count
4 DEG C of bacterium muds saved up to sewage treatment bacterium after number identification.
It preferably, further include 2~5g/L gel particles, 1~3mm of gel particles partial size, the gel in the initial incubation liquid
For one of sodium alginate gel, agar gel, carbomer gel, xanthan gum, Ago-Gel, polyacrylamide gel or
It is a variety of.
A method of high-ammonia-nitrogen sewage processing being carried out using above-mentioned immobilization biological reaction filter plate, includes following specific step
It is rapid:
(1) fully transparent sewage-treating reactor will be seal-installed on after the side polishing of immobilization biological reaction filter plate
In, it is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, keeps every layer of immobilization biological reaction filter
Plate is totally submerged;
(2) high-ammonia-nitrogen sewage is separated by solid-liquid separation, liquid is injected into dirt using up flow type after the filtering of 20~30cm rough sand
In water processing reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains 10~
30cm, liquid successively filter immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 0.3~
1h;
(3) after injecting sewage liquid, fluorescent lamp illumination is continuously given for 24 hours, and intensity of illumination is 1000~2500Lx;
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Preferably, the setting number of plies of the immobilization biological reaction filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤200mg/L
One layer of setting, 200~400mg/L are arranged two layers, and 400~600mg/L is arranged three layers, and so on;The high-ammonia-nitrogen sewage is solid
Aeration operation is carried out before liquid separation;Every layer of filter plate of immobilization biological reaction gives illumination, intensity of illumination respectively in the step (3)
1500Lx。
It is that the present invention obtains the utility model has the advantages that
1, using the porous deposited glass formed after glass molten drop spray cooling deposition as support carrier, same volume
Under large specific surface area, load also larger with the contact area of substrate liquid after PVA film, microorganism is fixed in PVA film layer, raw
Object availability is substantially improved, and promotes treatment effeciency.The pore size of deposited glass is moderate, take into account permeation filtration mobility and
Hydraulic detention time reduces the processing time of unit volume substrate while guaranteeing ammonia nitrogen elimination factor.
2, hard under glass material room temperature, for loading the mechanical strength after PVA film regardless of occlusion vehicle, use
The PVA of high polymerization degree is as embedded material, and viscosity is high, and caking property is strong, formed after PVA film can resistance to erosion, not easily to fall off, addition is received
The ductility and mechanical strength that PVA film can be dramatically increased after rice is silica modified, prevent PVA film from tearing.
3, PVA has good film forming, and the PVA film layer of deposited glass area load is thin, while joined alginic acid
Sodium and diatomite overcome the disadvantage of PVA material mass-transfer performance difference;Sodium alginate and diatomite are added as fixed constituent element is adsorbed
The fixed amount of microorganism can be increased in PVA film, microorganism fixed effect is stablized, not easily runed off, and fixes and to the activity of microorganism
It influences minimum, the high vigor of microorganism can be kept when using for a long time.
It 4, can be according to the ammonia nitrogen level flexible modulation filter plate of sewage when immobilization biological reaction filter plate is applied to sewage treatment
The number of plies changes processing intensity, reduces unnecessary waste, and efficient process high-ammonia-nitrogen sewage reduces processing cost.
5, horizontal by gradually increasing the ammonia nitrogen loading of sewage treatment bacterium, gradually domestication enrichment Non-aqueous processing bacterium, increases
The mineralized nitrogen activity that thallus is promoted while thalline quantity, obtains high activity sewage treatment bacterial.
6, when bacterium predominantly nitrifies or nitrite bacteria, it is substantially carried out aerobic nitrification or nitrosation reaction, due to exposing
The total embedding of gas and algae can provide oxygen for nitrification or nitrosation reaction, improve nitrification or nitrosation reaction rate, meanwhile, algae
Class can also fix ammonia nitrogen and phosphorus, carry out sewage purification, can reduce hydraulic detention time under the double purified processing of algae and bacterium,
It is obviously improved sewage treating efficiency.Under anoxia condition, denitrifying bacteria activity is promoted, in the condition without aeration operation and algae
Under can also carry out sewage treatment.
Detailed description of the invention
Fig. 1 immobilization biological reacts filter plate surface SEM electron microscope.
Specific embodiment
Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side
Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.
Embodiment 1: being prepared as follows and immobilization biological is applied to react filter plate:
One, the preparation of raw material and prefabricated
The degree of polymerization of pure PVA is 2000, alcoholysis degree 87%.
The bacterium mud acclimating of sewage treatment bacterium:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, dirt will be derived from the fermenter
The activated sludge of water treatment plant is that 2.19g/L accesses 50rpm stirring training in culture solution by mixed genetic-neural network (MLSS)
It supports, guarantees that condition of culture is constant: 14 DEG C of temperature, pH=7.0, dissolved oxygen 2.0mg/L;Ammonium nitrogen concentration is in initial incubation liquid
250mg/L, COD 100mg/L;
(B) every 6 hours half amounts replacement domestication culture solution after reaching 8g/L to MLSS is cultivated, first precipitates 20min before changing liquid, so
The sterile minimal media liquid of equivalent is added in removal supernatant afterwards, altogether domestication culture 48h;Ammonium nitrogen and chemistry in the domestication culture solution
Oxygen demand concentration is incremented by the basis of initial incubation liquid with replacement number, is incremented by 50mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count
4 DEG C of bacterium muds saved up to sewage treatment bacterium after number identification.(method: (1) Huang Jue nitrobacteria is referred to by culture identification
Separation and identification [J] aquatic science and technology information, 2004 (3): 130-134;(2) Jiang Xin fires the separation mirror of anaerobic denitrifying bacteria
Primary Study [D] fixed and its to aquiculture waste water denitrification), sewage treatment bacterium is mainly nitrobacteria, nitrosation
Bacterium and denitrifying bacteria, the thallus total concentration of nitrobacteria, nitrite bacteria and denitrifying bacteria is 1.56 × 10 in bacterium mud7
A/g..
Two, the preparation of immobilization biological reaction filter plate, includes following specific steps:
(1) colourless transparent glass raw material is heated to 700 DEG C of heat preservations, liquid glass is used into multilayer spray after being completely melt
It deposits plate preparation facilities and prepares deposited glass, spray deposition technology parameter are as follows: using 5MPa high pressure argon gas as atomization gas,
Vertical spray distance is 25cm, and drain bore is 6mm, and spray angle is 45 °, and sediment pan is horizontal positioned, and sediment pan level is moved
Dynamic speed is 2mm/s, and vertically moving down speed is 0.1mm/s, and sediment pan makees horizontal back and forth movement every 100s with identical speed, directly
Stop deposition when reaching 1cm to deposit thickness, deposit is immersed into cold water the deposited glass that cools down rapidly to obtain;Anti-condensation glass
Mean particle size is 0.4mm, and accumulation forms hole between glass particle, and the light transmittance of deposited glass is 75%.
(2) 6wt%PVA, 2wt% nano silica, 1wt% diatomite, 1wt% alginic acid are weighed by mass fraction
Sodium, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are completely molten to PVA, sodium alginate
Solution, is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, and ultrasonic degasification, then cold after mixing evenly
But PVA solution is obtained to room temperature;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, uses sewage treatment microorganism using bacterial sediment as fixed.
(4) will be cooled to room temperature PVA solution mixed with sewage treatment microorganism by weight 4:1 after 250rpm magnetic force stir
Mix 10min;Deposited glass is completely immersed in PVA mixed liquor immediately, 10kHz ultrasound degasification 5min;Deposited glass is taken out,
It is seal-installed on stainless steel ducting outlet, 0.4MPa wind pressure wind drenches PVA mixed solution extra in 5min removal hole;
At (5) 4 DEG C, 0.5wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after deposition
Glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and filtration time 0.5h takes out deposited glass
It is placed in solidification crosslinking 10h in 4 DEG C of refrigerator, with distilled water up flow type filtration washing 15min to get fixed metaplasia after solidification crosslinking
Object reacts filter plate, and immobilization biological reaction filter plate is placed in 4 DEG C, saves backup in the phosphate buffer of pH7.2.Using beauty
State's Defelsko PosiTector 200C Series Ultrasonic coating thickness detector measure deposit glass plate surface PVA film with a thickness of
56±3.5μm。
High-ammonia-nitrogen sewage processing is carried out using above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) it will be seal-installed in sewage-treating reactor after the side polishing of immobilization biological reaction filter plate, equidistantly
It is vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, and every layer of immobilization biological reaction filter plate is kept to soak completely
Not;The setting number of plies that immobilization biological reacts filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤one layer of 200mg/L setting, and 200
~400mg/L is arranged two layers, and 400~600mg/L is arranged three layers, and so on, the ammonia nitrogen value of high-ammonia-nitrogen sewage in the present embodiment
For 135.4mg/L, one layer of immobilization biological reaction filter plate is set and is filtered processing.
(2) high-ammonia-nitrogen sewage is directly separated by solid-liquid separation, liquid is injected into dirt using up flow type after the filtering of 20cm rough sand
In water processing reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains 10cm, liquid
Body successively filters immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 0.3h;
(3) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Embodiment 2: being prepared as follows and immobilization biological is applied to react filter plate:
One, the preparation of raw material and prefabricated
The culture chlorella that individually suspends prepares sewage treatment algae suspending nutrient solution, and alga cells are close in algae culture suspension
Degree is 1.22 × 105Stop culture when a/mL;
The degree of polymerization of pure PVA is 6000, alcoholysis degree 89%.
Two, the preparation of immobilization biological reaction filter plate, includes following specific steps:
(1) colourless transparent glass raw material is heated to 950 DEG C of heat preservations, liquid glass is used into multilayer spray after being completely melt
It deposits plate preparation facilities and prepares deposited glass, spray deposition technology parameter are as follows: using 10MPa high pressure argon gas as atomization gas
Body, vertical spray distance are 35cm, and drain bore is 8mm, and spray angle is 60 °, and sediment pan is horizontal positioned, and sediment pan is horizontal
Movement speed is 4mm/s, and vertically moving down speed is 0.2mm/s, and sediment pan makees horizontal back and forth movement every 100s with identical speed,
Until deposit thickness stops deposition when reaching 10cm, deposit is immersed into cold water the deposited glass that cools down rapidly to obtain;Condensation
Glass particle average grain diameter is 1.1mm, and accumulation forms hole between glass particle, and the light transmittance of deposited glass is 90%.
(2) 8wt%PVA, 4wt% nano silica, 3wt% diatomite, 3wt% alginic acid are weighed by mass fraction
Sodium, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are completely molten to PVA, sodium alginate
Solution, is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, and ultrasonic degasification, then cold after mixing evenly
But PVA solution is obtained to room temperature;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, algae is precipitated and uses sewage treatment microorganism as fixed;
(4) will be cooled to room temperature PVA solution mixed with sewage treatment microorganism by weight 20:1 after 500rpm magnetic force
Stir 20min;Deposited glass is completely immersed in PVA mixed liquor immediately, 20kHz ultrasound degasification 15min;Take out deposit glass
Plate, is seal-installed on stainless steel ducting outlet, and 0.8MPa wind pressure wind drenches PVA mixed solution extra in 20min removal hole;
At (5) 4 DEG C, 0.8wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after deposition
Glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and filtration time 1.5h takes out deposited glass
It is placed in solidification crosslinking 16h in 4 DEG C of refrigerator, with distilled water up flow type filtration washing 25min to get fixed metaplasia after solidification crosslinking
Object reacts filter plate, and immobilization biological reaction filter plate is placed in 4 DEG C, saves backup in the phosphate buffer of pH7.2, using beauty
State's Defelsko PosiTector 200C Series Ultrasonic coating thickness detector measure deposit glass plate surface PVA film with a thickness of
163±7.8μm。
High-ammonia-nitrogen sewage processing is carried out using above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) fully transparent sewage-treating reactor will be seal-installed on after the side polishing of immobilization biological reaction filter plate
In, it is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, keeps every layer of immobilization biological reaction filter
Plate is totally submerged;The setting number of plies that immobilization biological reacts filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤200mg/L setting
One layer, 200~400mg/L is arranged two layers, and 400~600mg/L is arranged three layers, and so on.High-ammonia-nitrogen sewage in the present embodiment
Ammonia nitrogen value be 388.4mg/L, two layers immobilization biological is set and reacts filter plate.
(2) it is separated by solid-liquid separation after high-ammonia-nitrogen sewage being aerated 2h, liquid is infused using up flow type after the filtering of 30cm rough sand
Enter in sewage-treating reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains
30cm, liquid successively filter immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 1h;
(3) after injecting sewage liquid, fluorescent lamp single light source illumination, intensity of illumination 1000Lx are continuously given for 24 hours;
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Embodiment 3: being prepared as follows and immobilization biological is applied to react filter plate:
One, the preparation of raw material and prefabricated
Individually suspend culture Nannochloropsis oculata, Wild Vitis species, scenedesmus preparation sewage treatment algae suspending nutrient solution, into plateau
It is centrifuged, is resuspended by pure water after weight in wet base ratio 2:2:3 mixing, algae cell density is 6.35 × 10 in re-suspension liquid respectively afterwards5A/mL,
The degree of polymerization of pure PVA is 4000, alcoholysis degree 88%.
The bacterium mud acclimating of sewage treatment bacterium:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, it in the fermenter will be active dirty
Mud is that 3.03g/L accesses 100rpm stir culture in culture solution by mixed genetic-neural network (MLSS), guarantees condition of culture
It is constant: 17 DEG C of temperature, pH=7.5, dissolved oxygen 3.0mg/L;Ammonium nitrogen concentration is 250mg/L, COD in initial incubation liquid
For 100mg/L;It further include 5g/L gel particles in initial incubation liquid, gel particles partial size 3mm, the gel is 20wt% sodium alginate
Hydrogel, nitrobacteria and nitrite bacteria have the habit of apposition growth, and attachment can be provided by increasing gel particles, improve bacterium
Body proliferation activity forms thallus micelle convenient for precipitating when changing liquid, prevents thallus streaming.
(B) culture solution is tamed in half amount replacement for every eight hours after culture reaches 8g/L to MLSS, first precipitates 40min before changing liquid, so
The sterile minimal media liquid of equivalent is added in removal supernatant afterwards, altogether domestication culture 72h;Ammonium nitrogen and chemistry in the domestication culture solution
Oxygen demand concentration is incremented by the basis of initial incubation liquid with replacement number, is incremented by 70mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count
4 DEG C of bacterium muds saved up to sewage treatment bacterium after number identification.By culture identification, sewage treatment bacterium predominantly nitrifies thin
Bacterium, nitrite bacteria and denitrifying bacteria, the cell concentration of nitrobacteria, nitrite bacteria and denitrifying bacteria is in bacterium mud
5.98×107A/g.
Two, the preparation of immobilization biological reaction filter plate, includes following specific steps:
(1) colourless transparent glass raw material is heated to 800 DEG C of heat preservations, liquid glass is used into multilayer spray after being completely melt
It deposits plate preparation facilities and prepares deposited glass, spray deposition technology parameter are as follows: using 7.5MPa high pressure argon gas as atomization gas
Body, vertical spray distance are 30cm, and drain bore is 7mm, and spray angle is 52 °, and sediment pan is horizontal positioned, and sediment pan is horizontal
Movement speed is 3mm/s, and vertically moving down speed is 0.15mm/s, and sediment pan makees horizontal round-trip fortune every 100s with identical speed
It is dynamic, until deposit thickness stops deposition when reaching 6cm, deposit is immersed into cold water the deposited glass that cools down rapidly to obtain;It is cold
Solidifying glass particle average grain diameter is 0.75mm, and accumulation forms hole between glass particle, and the light transmittance of deposited glass is 82%.
(2) 7wt%PVA, 3wt% nano silica, 2wt% diatomite, 2wt% alginic acid are weighed by mass fraction
Sodium, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are completely molten to PVA, sodium alginate
Solution, is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, and ultrasonic degasification, then cold after mixing evenly
But PVA solution is obtained to room temperature;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, uses sewage treatment microorganism as fixed after bacterial sediment and algae precipitating are mixed by weight in wet base ratio for 10:1;
(4) will be cooled to room temperature PVA solution mixed with sewage treatment microorganism by weight 12:1 after 350rpm magnetic force
Stir 15min;Deposited glass is completely immersed in PVA mixed liquor immediately, 15kHz ultrasound degasification 10min;Take out deposit glass
Plate, is seal-installed on stainless steel ducting outlet, and 0.6MPa wind pressure wind drenches PVA mixed solution extra in 13min removal hole;
At (5) 4 DEG C, 0.65wt%CaCl will be contained2Saturation boric acid solution uniformly filtered by up flow type it is heavy after wind leaching
Product glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and filtration time 1h takes out deposited glass
It is placed in solidification crosslinking 13h in 4 DEG C of refrigerator, with distilled water up flow type filtration washing 20min to get fixed metaplasia after solidification crosslinking
Object reacts filter plate, and immobilization biological reaction filter plate is placed in 4 DEG C, saves backup in the phosphate buffer of pH7.2, using beauty
State's Defelsko PosiTector 200C Series Ultrasonic coating thickness detector measure deposit glass plate surface PVA film with a thickness of
121±6.6μm。
High-ammonia-nitrogen sewage processing is carried out using above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) fully transparent sewage-treating reactor will be seal-installed on after the side polishing of immobilization biological reaction filter plate
In, it is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, keeps every layer of immobilization biological reaction filter
Plate is totally submerged;The setting number of plies that immobilization biological reacts filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤200mg/L setting
One layer, 200~400mg/L is arranged two layers, and 400~600mg/L is arranged three layers, and so on.High-ammonia-nitrogen sewage in the present embodiment
Ammonia nitrogen value be 558.9mg/L, three layers of immobilization biological reaction filter plates are set.
(2) it is separated by solid-liquid separation after high-ammonia-nitrogen sewage being aerated 6h, liquid is infused using up flow type after the filtering of 25cm rough sand
Enter in sewage-treating reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains
20cm, liquid successively filter immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 0.7h;
(3) after injecting sewage liquid, fluorescent lamp illumination is continuously given for 24 hours, and immobilization biological every layer of filter plate of reaction is given respectively
Give illumination, intensity of illumination 1500Lx.
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Embodiment 4: being prepared as follows and immobilization biological is applied to react filter plate:
One, the preparation of raw material and prefabricated
Individually suspend culture cyanobacteria, diatom, spirulina, red bacterium prepares sewage treatment algae suspending nutrient solution, into flat
Platform is centrifuged respectively after the phase, is resuspended by pure water after weight in wet base ratio 1:1:2:5 mixing, algae cell density is 4.11 × 10 in re-suspension liquid5
A/mL.
The degree of polymerization of pure PVA is 3000, alcoholysis degree 88%.
The bacterium mud acclimating of sewage treatment bacterium:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, it in the fermenter will be active dirty
Mud is that 2.58g/L accesses 75rpm stir culture in culture solution by mixed genetic-neural network (MLSS), guarantees that condition of culture is permanent
It is fixed: 16 DEG C of temperature, pH=7.3, dissolved oxygen 2.5mg/L;Ammonium nitrogen concentration is 250mg/L in initial incubation liquid, and COD is
100mg/L;It further include 3.5g/L gel particles in initial incubation liquid, gel particles partial size 2mm, the gel is solidifying for 10wt% agar
Glue.
(B) every 7 hours half amounts replacement domestication culture solution after reaching 8g/L to MLSS is cultivated, first precipitates 30min before changing liquid, so
The sterile minimal media liquid of equivalent is added in removal supernatant afterwards, altogether domestication culture 60h;Ammonium nitrogen and chemistry in the domestication culture solution
Oxygen demand concentration is incremented by the basis of initial incubation liquid with replacement number, is incremented by 60mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count
4 DEG C of bacterium muds saved up to sewage treatment bacterium after number identification.By culture identification, sewage treatment bacterium predominantly nitrifies thin
Bacterium, nitrite bacteria and denitrifying bacteria, nitrify in bacterium mud and/or the cell concentration of denitrifying bacteria is 3.89 × 107A/g.
Two, the preparation of immobilization biological reaction filter plate, includes following specific steps:
(1) colourless transparent glass raw material is heated to 850 DEG C of heat preservations, liquid glass is used into multilayer spray after being completely melt
It deposits plate preparation facilities and prepares deposited glass, spray deposition technology parameter are as follows: using 7.5MPa high pressure argon gas as atomization gas
Body, vertical spray distance are 30cm, and drain bore is 8mm, and spray angle is 60 °, and sediment pan is horizontal positioned, and sediment pan is horizontal
Movement speed is 4mm/s, and vertically moving down speed is 0.2mm/s, and sediment pan makees horizontal back and forth movement every 100s with identical speed,
Until deposit thickness stops deposition when reaching 8cm, deposit is immersed into cold water the deposited glass that cools down rapidly to obtain;Condense glass
Glass mean particle size is 0.9mm, and accumulation forms hole between glass particle, and the light transmittance of deposited glass is 88%.
(2) 7.5wt%PVA, 3.5wt% nano silica, 1wt% diatomite, 2wt% seaweed are weighed by mass fraction
Sour sodium, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are completely molten to PVA, sodium alginate
Solution, is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, and ultrasonic degasification, then cold after mixing evenly
But PVA solution is obtained to room temperature;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, uses sewage treatment microorganism as fixed after bacterial sediment and algae precipitating are mixed by weight in wet base ratio for 1:1.
(4) will be cooled to room temperature PVA solution mixed with sewage treatment microorganism by weight 10:1 after 400rpm magnetic force
Stir 12min;Deposited glass is completely immersed in PVA mixed liquor immediately, 15kHz ultrasound degasification 10min;Take out deposit glass
Plate, is seal-installed on stainless steel ducting outlet, and 0.5MPa wind pressure wind drenches PVA mixed solution extra in 18min removal hole;
At (5) 4 DEG C, 0.7wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after deposition
Glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and filtration time 1.2h takes out deposited glass
It is placed in solidification crosslinking 14h in 4 DEG C of refrigerator, with distilled water up flow type filtration washing 25min to get fixed metaplasia after solidification crosslinking
Object reacts filter plate, and immobilization biological reaction filter plate is placed in 4 DEG C, saves backup in the phosphate buffer of pH7.2, using beauty
State's Defelsko PosiTector 200C Series Ultrasonic coating thickness detector measure deposit glass plate surface PVA film with a thickness of
133±6.9μm。
High-ammonia-nitrogen sewage processing is carried out using above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) fully transparent sewage-treating reactor will be seal-installed on after the side polishing of immobilization biological reaction filter plate
In, it is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, keeps every layer of immobilization biological reaction filter
Plate is totally submerged;The setting number of plies that immobilization biological reacts filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤200mg/L setting
One layer, 200~400mg/L is arranged two layers, and 400~600mg/L is arranged three layers, and so on.High-ammonia-nitrogen sewage in the present embodiment
Ammonia nitrogen value be 615.2mg/L, four layers of immobilization biological reaction filter plates are set.
(2) it is separated by solid-liquid separation after high-ammonia-nitrogen sewage being aerated 4h, by liquid using upper after the filtering of 20~30cm rough sand
Formula is injected in sewage-treating reactor, and liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains
In 10~30cm, liquid successively filters immobilization biological reaction filter plate, and every layer of immobilization biological reacts filter plate hydraulic detention time
For 0.6h;
(3) after injecting sewage liquid, fluorescent lamp illumination, intensity of illumination 2500Lx are continuously given for 24 hours;
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Embodiment 5: being prepared as follows and immobilization biological is applied to react filter plate:
One, the preparation of raw material and prefabricated
Individually suspend culture chlorella, red bacterium prepare sewage treatment algae suspending nutrient solution, into plateau after respectively
Centrifugation is resuspended by pure water after weight in wet base ratio 1:3 mixing, and algae cell density is 5.29 × 10 in re-suspension liquid5A/mL.
The degree of polymerization of pure PVA is 5000, alcoholysis degree 87%.
The bacterium mud acclimating of sewage treatment bacterium:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, it in the fermenter will be active dirty
Mud is that 2.33g/L accesses 75rpm stir culture in culture solution by mixed genetic-neural network (MLSS), guarantees that condition of culture is permanent
It is fixed: 15 DEG C of temperature, pH=7.4, dissolved oxygen 2.2mg/L;Ammonium nitrogen concentration is 250mg/L in initial incubation liquid, and COD is
100mg/L;It further include 4g/L gel particles in initial incubation liquid, gel particles partial size 2mm, the gel is solidifying for 1.5wt% agarose
Glue.
(B) every 7 hours half amounts replacement domestication culture solution after reaching 8g/L to MLSS is cultivated, first precipitates 25min before changing liquid, so
The sterile minimal media liquid of equivalent is added in removal supernatant afterwards, altogether domestication culture 70h;Ammonium nitrogen and chemistry in the domestication culture solution
Oxygen demand concentration is incremented by the basis of initial incubation liquid with replacement number, is incremented by 65mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count
4 DEG C of bacterium muds saved up to sewage treatment bacterium after number identification.By culture identification, sewage treatment bacterium predominantly nitrifies thin
Bacterium, nitrite bacteria and denitrifying bacteria, the thallus total concentration of nitrobacteria, nitrite bacteria and denitrifying bacteria is in bacterium mud
4.42×107A/g.
Two, the preparation of immobilization biological reaction filter plate, includes following specific steps:
(1) glass raw material is heated to 900 DEG C of heat preservations, liquid glass is used into multi-layer spray deposition plate after being completely melt
Preparation facilities prepares deposited glass, spray deposition technology parameter are as follows: vertical to spray using 9MPa high pressure argon gas as atomization gas
Distance is 35cm, and drain bore is 7mm, and spray angle is 55 °, and sediment pan is horizontal positioned, and sediment pan horizontal movement velocity is
3mm/s, vertically moving down speed is 0.15mm/s, and sediment pan makees horizontal back and forth movement every 100s with identical speed, until deposition
Thickness degree stops deposition when reaching 9cm, and deposit is immersed in cold water the deposited glass that cools down rapidly to obtain;Anti-condensation glass particle is flat
Equal partial size is 0.8mm, and accumulation forms hole between glass particle, and the light transmittance of deposited glass is 81%.
(2) 7wt%PVA, 2wt% nano silica, 1wt% diatomite, 1.5wt% alginic acid are weighed by mass fraction
Sodium, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are completely molten to PVA, sodium alginate
Solution, is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, and ultrasonic degasification, then cold after mixing evenly
But PVA solution is obtained to room temperature;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering,
Resuspended bacterium solution or algae culture suspension are centrifuged 10min respectively at 2500rpm, bacterial sediment or algae is taken to precipitate 4 DEG C of guarantors respectively
It deposits, uses sewage treatment microorganism as fixed after bacterial sediment and algae precipitating are mixed by weight in wet base ratio for 6:1.
(4) will be cooled to room temperature PVA solution mixed with sewage treatment microorganism by weight 15:1 after 250rpm magnetic force
Stir 15min;Deposited glass is completely immersed in PVA mixed liquor immediately, 18kHz ultrasound degasification 11min;Take out deposit glass
Plate, is seal-installed on stainless steel ducting outlet, and 0.47MPa wind pressure wind drenches PVA mixed solution extra in 18min removal hole;
At (5) 4 DEG C, 0.6wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after deposition
Glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and filtration time 0.8h takes out deposited glass
It is placed in solidification crosslinking 12h in 4 DEG C of refrigerator, with distilled water up flow type filtration washing 20min to get fixed metaplasia after solidification crosslinking
Object reacts filter plate, and immobilization biological reaction filter plate is placed in 4 DEG C, saves backup in the phosphate buffer of pH7.2, using beauty
State's Defelsko PosiTector 200C Series Ultrasonic coating thickness detector measure deposit glass plate surface PVA film with a thickness of
129±3.8μm。
High-ammonia-nitrogen sewage processing is carried out using above-mentioned immobilization biological reaction filter plate, includes following specific steps:
(1) fully transparent sewage-treating reactor will be seal-installed on after the side polishing of immobilization biological reaction filter plate
In, it is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, keeps every layer of immobilization biological reaction filter
Plate is totally submerged;The setting number of plies that immobilization biological reacts filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤200mg/L setting
One layer, 200~400mg/L is arranged two layers, and 400~600mg/L is arranged three layers, and 600~800mg/L is arranged four layers, and so on.
The ammonia nitrogen value of high-ammonia-nitrogen sewage is 789.7mg/L in the present embodiment, and four layers of immobilization biological reaction filter plate are arranged.
(2) it is separated by solid-liquid separation after high-ammonia-nitrogen sewage being aerated 3h, liquid is infused using up flow type after the filtering of 28cm rough sand
Enter in sewage-treating reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains
25cm, liquid successively filter immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 0.8h;
(3) after injecting sewage liquid, fluorescent lamp illumination is continuously given for 24 hours, and immobilization biological every layer of filter plate of reaction is given respectively
Give illumination, intensity of illumination 1750Lx.
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, meets national standard heel row
It puts.
Embodiment 6: remaining is same as Example 4, the difference is that further including 3g/L solidifying in the initial incubation liquid
Micelle, gel particles partial size 3mm, the gel are the mixture of carbomer gel, xanthan gum, polyacrylamide gel, mixture
In carbomer gel containing 20wt%, 25wt% xanthan gum, 55wt% polyacrylamide gel.Carbomer gel concentration is 30%,
Xanthan gum concentration is 15%, polyacrylamide concentration 25%, is all made of pure water preparation, and co-grinding is matched after solidification and is
The broken gel particles of average grain diameter 3mm.
Comparative examples 1: ammonia oxidizing bacteria is fixed with according to the preparation of method disclosed in Chinese patent CN108164000A
Glass plate, as subsequent control group.
Comparative examples 2: detesting based on mesh carrier is prepared according to method disclosed in Chinese patent CN103951048A
Anaerobic ammonium oxidation bacteria adhension fixed type biological active filler, as subsequent control group.
Comparative examples 3: remaining is same as Example 5, the difference is that not adding any sewage treatment in PVA film
Microorganism.
For detection performance of the invention, following test experience is carried out:
1, immobilization biological reaction filter plate SEM Electronic Speculum detection.
The immobilization biological reaction filter plate prepared in Example 1 carries out the shooting of SEM electron-microscope scanning, the result is shown in Figure 1.
As shown in Figure 1, deposited glass is loosely stacked by numerous small glass molten drop solidifying bodies, spray deposition technology
So that glass molten drop is adhered to one another before solidification, then quickly solidification, stacks generate hole each other, forms porous glass plate.
The PVA of high polymerization degree has bigger viscosity, forms uniform film after wall built-up after the extra PVA solution of wind leaching removal
Layer, there is no the holes for blocking deposited glass.
2, the Pore size distribution of deposited glass
The deposited glass prepared in Example 1~5 measures sample as sample, using ASAP2010 or 2020 analyzers
The pore-size distribution of product, the results are shown in Table 1:
Pore-size distribution in 1 sample of table
Group | Hole pore diameter range (μm) |
Embodiment 1 | 149~337 |
Embodiment 2 | 413~674 |
Embodiment 3 | 333~542 |
Embodiment 4 | 321~559 |
Embodiment 5 | 298~422 |
3, BET pore analysis
The deposited glass prepared in Example 1~5 prepares comparative examples 2 as filler to be formed as sample
The reaction bed of 30cm thickness analyzes specific surface area using BET method and hole holds accounting, the results are shown in Table 2:
2 BET pore analysis result of table
SAlways: total specific surface area;VAlways: total pore volume;
In conjunction with Tables 1 and 2 data it is found that the deposited glass in the present invention since there are a large amount of holes so that than
Surface area and Kong Rongjun are larger, the adsorbable and fixed more PVA film containing microorganism, while when also increasing substrate filtering plate
With the haptoreaction area of microorganism, microorganism utilization rate and reaction efficiency are improved.And comparative examples 1 and 2 are solid
Carrier, unit volume specific surface area is minimum, and absorption and fixed microorganism are extremely limited, can not be compared with the present invention.Control
Even if embodiment 2 forms reaction bed as filler, specific surface area is also significantly lower than porous deposited glass.
4, the ammonia nitrogen removal frank detection of high-ammonia-nitrogen sewage
Comparative examples 2 are prepared to the reaction bed to form 10cm thickness as filler, are implemented using Examples 1 to 5 and control
The sewage water treatment method processing 1m provided in example 1~33The high-ammonia-nitrogen sewage of respective concentration, the water outlet that picks up that treated measure ammonia
Nitrogen content and COD calculate ammonium nitrogen removal rate:
Ammonium nitrogen removal rate (%)=(influent ammonia nitrogen content-water outlet ammonia-nitrogen content)/influent ammonia nitrogen content * 100%
It the results are shown in Table 3
The ammonia nitrogen removal Activity determination of 3 immobilization biological of table reaction filter plate
As seen from the results in Table 3, for Examples 1 to 5 in the case where hydraulic detention time (HRT) is shorter, ammonia nitrogen clearance rate is aobvious
It writes and is higher than comparative examples 1~3, and COD is significantly reduced, and shows that the present invention can efficient process high-ammonia-nitrogen sewage.It is right
According to sewage treatment microorganism is free of in embodiment 3, it is solid in PVA film to show that sewage treatment depends on after comparing with embodiment 5
Fixed activated sewage handles microorganism, and in the case where being free of sewage treatment microorganism, PVA, sodium alginate and diatomite etc. are carried
Body material hardly has ammonia nitrogen removal effect, and comparative examples 1 are due to being the micro- life of area load in monolith solid glass plate
Object, effectively contact and processing area are small, can not remove ammonia nitrogen in a short time, although the packed bed that comparative examples 2 are formed is solid
It is fixed whether there is or not water treatment micro-organism, but the mass-transfer performance of the significantly restricted macromolecule carrier for the treatment of effeciency, while specific surface area is also smaller,
Treatment effeciency is caused to be substantially less than Examples 1 to 5.When containing bacterium and algae simultaneously, better processing effect.
Embodiment 1 and 5 is measured according to the method described above and the sewage water treatment method of comparative examples 1~3 stops in different waterpower
The ammonia nitrogen removal frank under the time is stayed, the results are shown in Table 4.
Influence of 4 hydraulic detention time of table to ammonia nitrogen removal frank
Hydraulic detention time reflects microorganism and anhydrous reaction time, the optimal water power standing time of embodiment 1 and 5
In 1~1.5h, ammonia nitrogen removal frank can't be substantially improved in the extension of time thereafter, illustrate to have stably reached in 1~1.5h
The maximum processing capability of filter plate, and the optimal water power standing time of case of comparative examples 1~3 is in 3h or so, and maximum ammonia nitrogen removal
Rate is also significantly lower than embodiment 1 and 5, illustrates to have reached the maximum sewage treatment load of comparative examples 1~3 in 3h, processing
Effect is substantially less than embodiment 1 and 5.
For comparative examples 1 due to finite surface area, the microorganism of load is less, also smaller with the contact area of sewage, because
Ammonia nitrogen removal frank under this peak load is also failed to more than 10%, comparative examples 2 due to limited mass-transfer performance and material thickness,
Cause biological reactions rates lower, therefore descend ammonia nitrogen removal frank also below 60% at full capacity, comparative examples 3 are due to unsupported dirt
The generation of water treatment micro-organism, ammonia nitrogen removal effect relies primarily on suction-operated of the large area PVA film material to ammonia nitrogen, when long
Between handle after can return and spit ammonia nitrogen, therefore ammonia nitrogen removal frank reduces instead after more than 3h.
4, mass-transfer performance is tested
By in Examples 1 to 5 containing microorganism PVA mixed liquor or comparative examples 3 in be free of the PVA solution of microorganism
It is painted on solid glass plate surface, crosslinking Treatment forms the PVA film with same thickness in deposited glass, PVA film is soaked in
It is measured as sample for subsequent efficient coefficient in PBS.The PVA mixed liquor brushing in embodiment 5 is separately formed 1mm's
PVA film is as control sample.
According to document: optimization [J] of matrix diffusion coefficients and its mass-transfer performance in Guan Qingkun, Yang Hong .PVA gel
Environmental project journal, the measuring method measurement Examples 1 to 5 of the mass tranfer coefficient in 2017 (3) and comparative examples 2~3
The efficient coefficient of PVA film or Web materials.
It the results are shown in Table 4:
The efficient coefficient of 5 PVA film of table or Web materials
Comparative examples 3 and embodiment 5 compare it is found that the addition of microorganism influences very the mass tranfer coefficient of PVA film in table 5
It is small, the mass-transfer performance of carrier material is not influenced, and substrate and product can free in and out carrier, overcome PVA high molecular material mass transfer
Restriction effect of the performance difference to microbial reaction.Although film layer is thin can to improve mass-transfer performance, embodiment 1 in actual use~
The mechanical performance that PVA film is used alone under 5 film thickness is very poor, it is easy to which fracture is broken, so deposited glass is needed to be propped up
Support load.
The mass tranfer coefficient of Examples 1 to 5 changes less under the conditions of 60~140 μm of film thickness, and mass-transfer performance is stablized, but works as film
When thickness increases to 1mm, mass-transfer performance declines to a great extent, and shows that film thickness is affected to mass-transfer performance, can hinder when film layer is thicker
The directional diffusion for hindering substrate and product, limits biological reactions rates.The data comparison of embodiment 5 and comparative examples 2 it is found that
Equally in millimetre-sized situation, the mass-transfer performance of PVA carrier is also significantly better than control Web materials in the present invention, illustrates seaweed
The addition of sour sodium and diatomite also has certain contribution to the mass-transfer performance of macromolecule carrier.
In conclusion support carrier is used as using the porous deposited glass formed after glass molten drop spray cooling deposition,
Large specific surface area under same volume, load PVA film after it is also larger with the contact area of substrate liquid, microorganism is fixed on PVA
In film layer, bioavilability is substantially improved, and promotes treatment effeciency.The pore size of deposited glass is moderate, takes into account permeation filtration
Mobility and hydraulic detention time, while guaranteeing ammonia nitrogen elimination factor reduce unit volume substrate the processing time.Glass
It is hard under material room temperature, for loading the mechanical strength after PVA film regardless of occlusion vehicle, using the PVA of high polymerization degree
As embedded material, viscosity is high, and caking property is strong, formed after PVA film can resistance to erosion, it is not easily to fall off, nano silica is added and changes
The ductility and mechanical strength that PVA film can be dramatically increased after property, prevent PVA film from tearing.PVA has good film forming, deposition
The PVA film layer of glass pane surface load is thin, while joined the disadvantage that sodium alginate overcomes PVA material mass-transfer performance difference;Sea
The fixed amount that can increase microorganism, microorganism fixed effect are added in PVA film as the fixed constituent element of absorption for mosanom and diatomite
Stablize, not easily runs off, it is fixed and minimum to the activity influence of microorganism, the high vigor of microorganism can be kept when using for a long time.
When immobilization biological reacts filter plate applied to sewage treatment, it can be changed according to the ammonia nitrogen level flexible modulation filter plate number of plies of sewage
Intensity is handled, unnecessary waste is reduced, efficient process high-ammonia-nitrogen sewage reduces processing cost.By gradually increasing at sewage
The ammonia nitrogen loading for managing bacterium is horizontal, gradually domestication enrichment Non-aqueous processing bacterium, and the ammonia nitrogen of thallus is promoted while increasing thalline quantity
Activity of conversion obtains high activity sewage treatment bacterial.When bacterium predominantly nitrification or nitrite bacteria, it is substantially carried out aerobic nitrification
Or nitrosation reaction improves nitrification or Asia since the total embedding of aeration and algae can provide oxygen for nitrification or nitrosation reaction
Nitration reaction rate, meanwhile, algae can also fix ammonia nitrogen and phosphorus, carry out sewage purification, the double purified processing of algae and bacterium
Under can reduce hydraulic detention time, be obviously improved sewage treating efficiency.Under anoxia condition, denitrifying bacteria activity is promoted, In
It is operated without aeration and sewage treatment can also be carried out under conditions of algae.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within;The technology that the present invention is not directed to can be realized by the prior art.
Claims (8)
1. a kind of immobilization biological reacts filter plate, it is characterised in that: described heavy comprising deposited glass and sewage treatment microorganism
Product glass plate is bonded by depositing after glass molten drop rapid condensation, and anti-condensation glass mean particle size is 0.4~1.1mm, glass
Accumulation forms hole between glass particle, and hole pore diameter range is 149~674 μm, the deposited glass with a thickness of 1~10cm,
Deposited glass inner and outer surfaces uniform load has one layer of PVA film, the PVA film with a thickness of 56~163 μm, it is fixed in PVA film
There is sewage treatment microorganism, the sewage treatment microorganism is sewage treatment bacterium and/or sewage treatment algae.
2. a kind of immobilization biological according to claim 1 reacts filter plate, it is characterised in that: the sewage treatment bacterium
For nitrobacteria, nitrite bacteria and denitrifying bacteria, the sewage treatment algae includes chlorella, cyanobacteria, diatom, spiral
One of algae, red bacterium, Nannochloropsis oculata, Wild Vitis species, scenedesmus are a variety of, and the light transmittance of the deposited glass is 75~
The degree of polymerization of 90%, the PVA are 2000~6000, alcoholysis degree 87~89%.
3. a kind of preparation method of immobilization biological reaction filter plate as claimed in claim 1 or 2, which is characterized in that comprising as follows
Specific steps:
(1) glass raw material is heated to 700~950 DEG C of heat preservations, liquid glass is used into multi-layer spray deposition plate after being completely melt
Material preparation facilities prepares deposited glass, spray deposition technology parameter are as follows: using 5~10MPa high pressure argon gas as atomization gas, hangs down
Straight spray distance is 25-35cm, and drain bore is 6~8mm, and spray angle is 45 °~60 °, and sediment pan is horizontal positioned, deposition
Disk horizontal movement velocity is 2~4mm/s, and vertically moving down speed is 0.1~0.2mm/s, and sediment pan is every 100s with identical speed
Make horizontal back and forth movement, until deposit thickness stops deposition when reaching 1~10cm, deposit is immersed in cold water and is cooled down rapidly
Obtain deposited glass;
(2) 6~8wt%PVA, 2~4wt% nano silica, 1~3wt% diatomite, 1~3wt% are weighed by mass fraction
Sodium alginate, surplus are water, pure PVA, sodium alginate powder are added in pure water, 95 DEG C of heating water baths are complete to PVA, sodium alginate
Fully dissolved is cooled to 35 DEG C of heat preservations, and by nano silica, diatomite slowly stirs addition, after mixing evenly ultrasonic degasification, with
After be cooled to room temperature to obtain PVA solution;
(3) 1 × PBS of the bacterium mud of the bacterium containing sewage treatment is resuspended, is homogenized and obtains resuspended bacterium solution after mono layer gauze filtering, will weighed
Outstanding bacterium solution or algae culture suspension take bacterial sediment or algae to precipitate 4 DEG C of preservations respectively respectively at 2500rpm centrifugation 10min, will
Bacterial sediment and/or algae precipitating are used as fixed with sewage treatment microorganism;
(4) it will be cooled to 250~500rpm after the PVA solution of room temperature is mixed with sewage treatment microorganism by weight 4~20:1
10~20min of magnetic agitation;Deposited glass is completely immersed in PVA mixed liquor immediately, 10~20kHz ultrasound degasification 5~
15min;Deposited glass is taken out, stainless steel ducting outlet is seal-installed on, 0.4~0.8MPa wind pressure wind drenches 5~20min removal
Extra PVA mixed solution in hole;
At (5) 4 DEG C, 0.5~0.8wt%CaCl will be contained2Saturation boric acid solution by up flow type uniformly filter wind leaching after deposition
Glass plate, the saturation boric acid solution are totally submerged entire deposit glass plate bulk, and 0.5~1.5h of filtration time takes out deposition
Glass plate is placed in 4 DEG C of refrigerator solidification 10~16h of crosslinking, after solidification crosslinking with distilled water up flow type filtration washing 15~
25min reacts filter plate to get immobilization biological, and immobilization biological reaction filter plate is placed in 4 DEG C, the phosphate-buffered of pH7.2
It is saved backup in liquid.
4. a kind of immobilization biological according to claim 3 reacts filter plate preparation method, it is characterised in that: described containing dirt
In the bacterium mud of water process bacterium the thallus total concentration of nitrobacteria, nitrite bacteria and denitrifying bacteria be 1.56~5.98 ×
107A/g, algae cell density is 1.22~6.35 × 10 in the algae culture suspension5A/mL;At fixation sewage
When reason microorganism includes bacterial sediment and algae precipitating, the weight in wet base ratio of bacterial sediment and algae precipitating is 1~10:1.
5. a kind of immobilization biological according to claim 3 reacts filter plate preparation method, it is characterised in that: the step
(1) further include sewage treatment bacterium bacterium mud acclimating step, it is specific as follows:
(A) sewage treatment bacterium is tamed and is enriched with using sterile initial incubation liquid, in the fermenter pressed activated sludge
MLSS is that 2.19~3.03g/L accesses 50~100rpm stir culture in culture solution, guarantees that condition of culture is constant: temperature 14-17
DEG C, pH=7.0~7.5, dissolved oxygen 2.0-3.0mg/L;Ammonium nitrogen concentration is 250mg/L, chemical oxygen demand in the initial incubation liquid
Amount is 100mg/L;
(B) culture solution is tamed in the replacement of every 6~8 hours half amounts after culture reaches 8g/L to MLSS, change before liquid and first precipitate 20~
Then 40min removes supernatant and the sterile minimal media liquid of equivalent is added, altogether 48~72h of domestication culture;In the domestication culture solution
Ammonium nitrogen and COD concentration are incremented by the basis of initial incubation liquid with replacement number, are incremented by 50~70mg/L every time;
(C) domestication culture after centrifuging and taking precipitate, will precipitating with 10 times of weight brines three times after, abandon supernatant, count reflect
4 DEG C of bacterium muds saved up to sewage treatment bacterium after fixed.
6. a kind of immobilization biological according to claim 5 reacts filter plate preparation method, it is characterised in that: described initial
Further include 2~5g/L gel particles in culture solution, 1~3mm of gel particles partial size, the gel be sodium alginate gel, agar gel,
One of carbomer gel, xanthan gum, Ago-Gel, polyacrylamide gel are a variety of.
7. a kind of method for carrying out high-ammonia-nitrogen sewage processing using the reaction filter plate of immobilization biological described in claims 1 or 2,
It is characterized in that, includes following specific steps:
(1) it will be seal-installed in fully transparent sewage-treating reactor after the side polishing of immobilization biological reaction filter plate,
It is equidistantly vertically arranged immobilization biological reaction filter plate, up flow type pre-installs 1 × PBS, every layer of immobilization biological is kept to react filter plate
It is totally submerged;
(2) high-ammonia-nitrogen sewage is separated by solid-liquid separation, liquid is injected at sewage using up flow type after the filtering of 20~30cm rough sand
It manages in reactor, liquid level is totally submerged every layer of immobilization biological reaction filter plate upper surface, and liquid level maintains 10~30cm, liquid
Body successively filters immobilization biological reaction filter plate, and every layer of immobilization biological reaction filter plate hydraulic detention time is 0.3~1h;
(3) after injecting sewage liquid, fluorescent lamp illumination is continuously given for 24 hours, and intensity of illumination is 1000~2500Lx;
(4) the purified water outlet of sewage-treating reactor carries out ammonia nitrogen value and chemical oxygen demand detection, discharges after meeting national standard.
8. a kind of method of the processing of immobilized enzyme hydrolysis described in claim 7, it is characterised in that: the immobilization biological reaction
The setting number of plies of filter plate is directly proportional to ammonia nitrogen value, ammonia nitrogen value≤one layer of 200mg/L setting, two layers of 200~400mg/L setting, and 400
~600mg/L is arranged three layers, and so on;The high-ammonia-nitrogen sewage carries out aeration operation before being separated by solid-liquid separation;In the step (3)
Immobilization biological every layer of filter plate of reaction gives illumination, intensity of illumination 1500Lx respectively.
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